Supercritical polymerization process and polymers produced therefrom

ABSTRACT

This invention relates to a process to produce propylene polymers comprising contacting a metallocene catalyst compound and an activator in a reaction medium comprising propylene, from 0 to 30 volume % of one or more solvents and from 0 to 30 mole % of one or more comonomers, under temperature and pressure conditions below the melting point of the propylene polymer and where:
         a) the temperature is at or above the critical temperature for the reaction medium, and the pressure is at least 500 kPa above the critical pressure of the reaction medium; or   b) the temperature is 1° C. or more above the critical temperature for the reaction medium, and the pressure is at or above the critical pressure of the reaction medium; or   c) the temperature is 1° C. or more above the critical temperature for the reaction medium, and the pressure is at least 500 kPa above the critical pressure of the reaction medium.

PRIORITY CLAIM

This application claims priority to U.S. Ser. No. 60/431,077, filed Dec.5, 2002.

BACKGROUND OF INVENTION

1. Field of Invention

The present invention relates to branched crystalline polymers,preferably polypropylene (BCPP) compositions and supercriticalpolymerization processes for the preparation of such compositions.

2. Description of Related Art

Various processes have been proposed for making polypropylenecompositions. Such different processes will typically have differentvariables and parameters, including different monomer compositions,solvents, additives, reaction conditions, catalyst systems, etc. Theproperties and characteristics of the final product have a great deal todo with the process variables and parameters that are selected, and ithas been recognized that small modifications in such variables andparameters can create significant differences in not only the finalproduct, e.g., polymer properties, but also in the effectiveness of theoverall process, e.g., catalyst productivity, presence or absence ofgel.

An ongoing need exists for processes that provide polypropylene withgood processability and high melt strength, which is desirable forapplications such as thermoforming, foaming, and blow molding. Poor meltstrength of polypropylenes shows up as excess sag in sheet extrusion,rapid thinning of walls in parts thermoformed in the melt phase, lowdraw-down ratios in extrusion coating, poor bubble formation inextrusion foam materials, and relative weakness in large-part blowmolding. Thus, it would be highly desirable to produce a polypropylenehaving enhanced melt strength as well as commercially valuableprocessability.

Furthermore, a need exists for a relatively straightforward method ofpreparing polypropylene having desirable properties, particularly amethod for making a branched polymer that does not require the use of across-linking agent, e.g., post-polymerization treatments, or the use ofcomonomers that have been found to result in undesirable gel formation,such as certain types of diene comonomers. Finally, there is a need fora process demonstrating high catalyst productivity in forming thepolymers described herein.

Additional references of interest include: U.S. Pat. No. 6,084,041, U.S.Pat. No. 5,969,062, U.S. Pat. No. 5,408,017, WO 93/11171, U.S. Pat. No.6,355,741, WO 92/14766, U.S. Pat. No. 5,326,835, German Application DE4,130,299 (equivalent to CA 2,118,711), Olefin Polymerization UsingHighly Congested ansa-Metallocenes under High Pressure: Formation ofSuperhigh Molecular Weight Polyolefins, Suzuki, et al., Macromolecules,2000, 33, 754-759, EP 1 123 226, WO 00 12572, WO 00 37514, EP 1 195 391,U.S. Pat. No. 6,355,741, and Ethylene Bis(Indenyl)Zirconocenes . . . ,Schaverien, C. J. et al., Organometallics, ACS, Columbus Ohio, vol 20,no. 16, August 2001, pg. 3436-3452, WO 96/34023, WO 97/11098, U.S. Pat.No. 5,084,534, U.S. Pat. No. 2,852,501, WO 93/05082, EP 129 368 B1, WO97/45434, JP 96-208535 199660807, U.S. Pat. No. 5,096,867, WO 96/12744,U.S. Pat. No. 5,408,017, U.S. Pat. No. 5,084,534, U.S. Pat. No.6,225,432, WO 02/090399, EP 1 195 391, WO 02/50145, US 2002 013440, WO01/46273, JP 10110003, and EP 1 008 607; JP 101 1003; and JP 3421202.

Another item of interest is an abstract obtained from the Borealiswebsite that stated:

-   -   Barbo Loefgren, E. Kokko, L. Huhtanen, M Lahelin, Petri Lehmus,        Udo Stehling “Metallocene-PP produced under supercritical        conditions.” 1st Bluesky Conference on Catalytic Olefin        Polymerization, 17.-20.6.2002, Sorrrento, Italy., ( ), 2002.        “mPP produced in bulk conditions (100% propylene), especially at        elevated temperature and under supercritical conditions, shows        rheological behaviour indicative for small amounts of LCB in the        polymer. This is a feature that can be utilized to produce mPP        with enhanced melt strength under industrially meaningful        conditions.”

SUMMARY OF INVENTION

This invention relates to a process to produce propylene polymerscomprising contacting a metallocene catalyst compound and an activatorin a reaction medium comprising propylene, from 0 to 30 volume % of oneor more solvents and from 0 to 30 mole % of one or more comonomers,under temperature and pressure conditions below the melting point of thepropylene polymer and where:

-   -   a) the temperature is at or above the critical temperature for        the reaction medium, and the pressure is at least 500 kPa above        the critical pressure of the reaction medium; or    -   b) the temperature is 1° C. or more above the critical        temperature for the reaction medium, and the pressure is at or        above the critical pressure of the reaction medium; or    -   c) the temperature is 1° C. or more above the critical        temperature for the reaction medium, and the pressure is at        least 500 kPa above the critical pressure of the reaction        medium, provided that when the metallocene catalyst compound is        1,2-ethylene bis(indenyl)zirconium di chloride supported on        silica or the metallocene catalyst compound is        dimethylsilylbis(indenyl) zirconium dichloride supported on        silica then the activator is not methyl alumoxane.

This invention further relates to the polymers produced by the aboveprocess.

DETAILED DESCRIPTION

In one or more specific embodiments, a process of preparing a polymercomposition that includes branched crystalline polypropylene isdescribed, which includes: contacting a metallocene catalyst compoundwith a polymerization medium that includes propylene monomers; andconducting polymerization of the propylene monomers under supercriticalconditions for a time sufficient to provide branched crystallinepolypropylene that has from 0.0 wt % to 2.0 wt % ethylene and a heat offusion of 70 J/g or more.

Also described is a process of preparing a polymer composition thatincludes branched crystalline polypropylene, which includes: combining ametallocene catalyst compound with propylene monomers in apolymerization medium having less than 30 volume percent diluent;conducting polymerization of the propylene monomers in thepolymerization medium at a reaction temperature of over 92° C. to formbranched crystalline polypropylene; and recovering a branchedcrystalline polypropylene that has from 0.0 wt % to 2.0 wt % ethyleneand a heat of fusion of 70 J/g or more.

Also described is a process of preparing a branched crystallinepolypropylene composition, which includes: contacting a polymerizationmixture that includes propylene monomers and less than 30 volume percentdiluent with a bridged metallocene compound that has at least twoindenyl rings or derivatives of indenyl rings, each ring beingsubstituted at the 2 and 4 positions; and conducting polymerization ofthe propylene monomers under supercritical conditions for a timesufficient to form a branched crystalline polypropylene compositionhaving a heat of fusion of 70 J/g or more.

Also described herein is a process of preparing a branched crystallinepolypropylene composition, which includes: combining a catalyst systemthat includes at least a metallocene compound with a polymerizationmixture that includes propylene monomers and less than 30 volume percentdiluent in a reactor system, and carrying out polymerization of thepropylene monomers in the reactor system under supercritical conditionsfor a time sufficient to form a branched crystalline polypropylene, inwhich the metallocene compound is represented by the formula:

wherein:

-   -   M¹ is selected from the group consisting of titanium, zirconium,        hafnium, vanadium, niobium, tantalum, chromium, molybdenum and        tungsten;    -   R¹ and R² are identical or different, and are one of a hydrogen        atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl        group, a C₆-C₁₀ aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀        alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl        group, a C₈-C₄₀ arylalkenyl group, an OH group or a halogen        atom; R¹ and R² may also be joined together to form an        alkanediyl group or a conjugated C₄₋₄₀ diene ligand which is        coordinated to M¹ in a metallocyclopentene fashion; R¹ and R²        may also be identical or different conjugated dienes, optionally        substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl        groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups,        said dienes having up to 30 atoms not counting hydrogen and        forming a π complex with M, examples include        1,4-diphenyl-1,3-butadiene, 1,3-pentadiene,        2-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene,        1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene,        1,4-bis(trimethylsilyl)-1,3-butadiene, and        1,4-dinaphthyl-1,3-butadiene;    -   Each R³ is identical or different from the other R³ and is each        a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group which may        be halogenated, a C₆-C₁₀ aryl group which may be halogenated, a        C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀        alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′,        —OR′, —OSiR′₃ or —PR′₂ radical, wherein R′ is one of a halogen        atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;    -   R⁴ to R¹² are identical or different and are hydrogen, or are as        defined for R³ or two or more adjacent radicals R⁵ to R⁷        together with the atoms connecting them form one or more rings;

—B(R¹⁴)—, ⁻Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴)—;

-   -   wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a        hydrogen atom, a halogen atom, a C₁-C₂₀ branched or linear alkyl        group, a C₁-C₂₀ fluoroalkyl or silaalkyl group, a C₆-C₃₀ aryl        group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, a        C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀        arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵,        together with the atoms binding them, form a cyclic ring;

-   -   or, R¹³ is represented by the formula:    -   wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more        adjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together        with the atoms connecting them form one or more rings;    -   M² is one or more carbons, silicon, germanium or tin; and    -   R⁸, R⁹, R¹⁰, R¹¹ and R¹² are identical or different and have the        meanings stated for R⁴ to R⁷.

Various specific embodiments, versions and examples of the inventionwill now be described, including preferred embodiments and definitionsthat are adopted herein for purposes of understanding the claimedinvention. It is understood, however, that for purposes of assessinginfringement, the scope of the “invention” will refer to the appendedclaims, including their equivalents, and elements or limitations thatare equivalent to those that are recited. All references to the“invention” below are intended to distinguish claimed compositions andmethods from compositions and methods not considered to be part of thisinvention. It is understood, therefore, that any reference to the“invention” may refer to one or more, but not necessarily all, of theinventions defined by the claims. References to specific “embodiments”are intended to correspond to claims covering those embodiments, but notnecessarily to claims that cover more than those embodiments.

Definitions and Properties

Certain terms and properties, some of which appear in the claims, willnow be defined, as used in this patent and for purposes of interpretingthe scope of the claims. To the extent a term used in a claim is notdefined below, it should be given the broadest definition persons in thepertinent art have given that term as reflected in printed publicationsand issued patents.

For purposes of this invention and the claims thereto, the criticaltemperatures (Tc) and critical pressures (Pc) are found in the Handbookof Chemistry and Physics, David R. Lide, Editor-in-Chief, 82nd edition2001-2002, CRC Press, LLC. New York, 2001.

In particular the Tc and Pc of various molecules are:

Tc Pc Pc Name (° K.) (MPa) Name Tc (° K.) (MPa) Hexane 507.6 3.025Propane 369.8 4.248 Isobutane 407.8 3.640 Toluene 591.8 4.11 Ethane305.3 4.872 Methane 190.56 4.599 Cyclobutane 460.0 4.98 Butane 425.123.796 Cyclopentane 511.7 4.51 Ethylene 282.34 5.041 1-butene 419.5 4.02Propylene 364.9 4.60 1-pentene 464.8 3.56 Cyclopentene 506.5 4.80Pentane 469.7 3.370 Isopentane 460.4 3.38 Benzene 562.05 4.895Cyclohexane 553.8 4.08 1-hexene 504.0 3.210° C.=273.2° K.

As used herein, the term “solvent” is defined broadly, to refer to anyliquid medium in which any of the polymerization reactions describedherein can take place, but not including any liquid material that ispolymerized, such as monomers. The term “solvent” includes diluents,which are preferably inert, and specifically includes the solvents anddiluents disclosed in Weng et al., U.S. Pat. No. 6,225,432.

The definition of the term “reactor system” used herein is any vessel,structure, enclosure, or combinations thereof in which a polymerizationreaction is capable of taking place, and also includes any vessel orcombination of vessels in which the various polymerization processesdescribed herein take place, in whole or in part. A reactor system canthus be or include a single reactor vessel, or multiple reactor vessels,e.g., series or parallel reactors.

The term “metallocene” is defined broadly as a compound represented bythe formula Cp_(m)MR_(n)Xq. The symbol “Cp” refers to either acyclopentadienyl ring, which may be substituted or unsubstituted, or acyclopentadienyl ring derivative, such as an indenyl ring, which mayalso be substituted or unsubstituted. As discussed in greater detailbelow, a preferred metallocene compound includes two cyclopentadienylrings, is sometimes referred to as a “bis-cyclopentadienyl” metallocene,and preferred cyclopentadienyl derivatives are bis-indenyl andbis-tetrahydroindenyl metallocene compounds. The symbol “M” refers to aGroup 4, 5, or 6 transition metal, for example, titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten.The symbol “R” in the general formula above refers to a hydrocarbylgroup, e.g., methyl, or a hydrocarboxy group, each of which may havefrom one to 20 carbon atoms. The symbol “X” refers to a halogen, e.g.,chlorine, bromine, or fluorine. The letter “m” can represent 1, 2, or 3;the letter “n” can represent 0, 1, 2, or 3; and the letter “q” canrepresent 0, 1, 2, or 3. The sum of m+n+q should be equal to theoxidation state of the transition metal. Examples of metallocenecompounds are found in U.S. Pat. Nos. 4,530,914; 4,542,199; 4,769,910;4,808,561; 4,871,705; 4,892,851; 4,933,403; 4,937,299; 5,017,714;5,057,475; 5,120,867; 5,132,381; 5,155,080; 5,198,401; 5,278,119;5,304,614; 5,324,800; 5,350,723; 5,391,790; 6,376,410; 6,376,412;6,380,120; 6,376,409; 6,380,122; and 6,376,413. The portions of thosepatents describing the metallocene compounds and the ingredients andprocedures for making and using such compounds are incorporated hereinby reference. As discussed in greater detail below, preferredmetallocene catalyst compounds are subsets of the general metallocenecategory, particularly those that provide the desired combinations ofproperties, as well as those that have demonstrated remarkably highproductivities.

An important feature of one or more specific embodiments of theinvention relates to the formation of crystalline polymers that are“branched,” at least to some degree. Various procedures have beenpublished, and either are or will be available to identify whether apolymer is branched or not, and a polymer is regarded herein as being“branched” to the extent branching can be detected, regardless of themethod or equipment used for such detection. Preferably, the crystallinepolypropylene is branched to a degree that it can be measuredquantitatively, and even more preferably expressed in terms of abranching index. A well known branching index for monodisperse polymersis used herein, referred to herein as “Branching Index,” also known asg′, which is defined as the ratio of intrinsic viscosities of thebranched to linear molecules, i.e., g′=[η]_(br)/[η]_(lin.) The term “η”stands for intrinsic solution viscosity. The term “[η]_(br)” is theintrinsic viscosity for the branched polymer molecule, and the term“[η]_(lin)” is that for a linear polymer molecule of equal molecularweight. For polydisperse samples the Branching Index is an averagebranching index, <g′>_(avg), defined as:

${< g^{\prime} >_{avg}} = {\frac{\lbrack\eta\rbrack_{branched}}{\lbrack\eta\rbrack_{linear}} = \frac{\sum\limits_{i = 1}^{N}\;{C_{i} \times \lbrack\eta\rbrack_{i}}}{\sum\limits_{i = 1}^{N}\;{C_{i} \times \left\lbrack {k \times M_{i}^{a}} \right\rbrack}}}$

Here, the index i refers to a given polymer fraction, M_(i) is themolecular weight of that fraction as measured by light scattering,[η]_(i) is the intrinsic viscosity of that fraction measured byviscometry, C_(i) is the concentration of that fraction, and “k” and “a”are the Mark Houwink coefficients for a linear polymer of the samechemical species. These quantities are measured by a GPC setup withonline light scattering, viscometer, and concentration detectors. Apolymer sample having branching will have intrinsic viscosity thatdeviates from that of a linear polymer. If a polymer sample is linear,the branching index, g′, will be 1.0 (+/−0.02). If a polymer sample isbranched, the average branching index will be less than 1. A lowerbranching index indicates more branching. In practice, average deviationlevels can be calculated from GPC-3D method involving three differentdetectors on line—LALLS, Viscometry, DRI—to measure, respectively, themolecular weights, viscosity, and concentration of the polymer solution.First, the GPC-LALLS data is used to measure molecular weight averages(M_(w), M₂). The respective intrinsic viscosity of the polymer solution,“η” is obtained from the viscometer data while the concentration at eachdata point is provided by the DRI technique. Finally the “η” is relatedto absolute molecular weight. Weight-average values of g′ are to becalculated from the data points that fall in the range of from thecharacteristic M_(w) of the polymer examined to the upper limit of2,000,000 Daltons. For any case in which some values of M_(w) are below100,000 Daltons, the weight average is calculated using only thosepoints between 100,000 Daltons and 2,000,000 Daltons. To calculate thebranching index for polypropylene that includes at least some ethylenemonomer units, the following equations should be used: g′=1.18 w, where“w” is the weight fraction of ethylene.

As used herein, the term “polypropylene” means a polymer made of atleast 50% propylene units, preferably at least 70% propylene units, morepreferably at least 80% propylene units, even more preferably at least90% propylene units or 95% propylene units, and most preferablyessentially 100% propylene units, which polypropylene is referred to asa “homopolymer.” In one or more specific embodiments described herein, a“polypropylene” referenced herein may have 65 wt % or more propylene; or80 wt % or more propylene; or 90 wt % or more propylene; or 97 wt % ormore propylene.

A polypropylene polymer made according to the processes described hereinis distinguishable from polymers that are sometimes described in thescientific or patent literature as “polypropylene” but which containundesirably high levels of ethylene. It has been recognized that evenrelatively small amounts of ethylene monomer can have a significant orsubstantial effect on final polymer properties. Accordingly, as usedherein, the term “polypropylene” also refers to a polypropylene polymerwith no more than 3.0 wt % ethylene; or no more than 2.5 wt % ethylene.Preferably, the polypropylenes described herein have no more than 2.0 wt% ethylene; or no more than 1.5 wt % ethylene; or no more than 1.0 wt %ethylene.

As used herein, the term “linear polypropylene” means a polypropylenehaving no detectable branching (quantitatively or qualitatively),preferably a Branching Index of 1.0 (+/−0.02).

As used herein, the term “branched polypropylene” (BCPP) means apolypropylene that is branched (detected quantitatively orqualitatively), and preferably has a Branching Index, based on measureddata, of less than 1.0 (+/−0.02).

As used herein, the term “polymerization medium” (also called reactionmedium) includes at least the monomers that form the polypropylenepolymer, and may also include solvents (including diluents), which arepreferably present only in a limited amount. For example, for bulkpolymerization embodiments of the processes, the amount of solvent(including diluents) is preferably negligible or even nonexistent, butthe polymerization medium may optionally include amounts of solvent,preferably as specified herein. After polymerization has begun, the term“polymerization medium” also includes any products of polymerization,e.g., macromer polymers as well as the final polypropylene product,e.g., a branched crystalline polypropylene. The term “polymerizationmedium” does not include any part of the catalyst system, e.g., catalystcompounds, supports, activators, or scavengers. In certain embodimentsof the process, the polymerization is conducted at temperatures abovethe critical temperature, e.g., temperatures ranging from 93° C. andabove; or 95° C. and above; or 98° C. and above; or at 100° C. andabove. The critical point for a particular polymerization medium canvary, depending on such factors as the particular monomers present inthe system, e.g., whether only propylene is present, or whether othermonomers are also present; the monomer concentration, e.g., whether asolvent/diluent is present and if so, how much is present; and thetemperature of the polymerization medium, e.g., reaction temperature.The critical temperature of pure polypropylene is considered to be 91.7°C., so that a polymerization conducted at 92° C., with pure propylene,should be operating at supercritical conditions. Any change in themonomers, or monomer concentration (e.g., presence of solvent/diluent)at that temperature, may affect whether supercritical conditions exist.In one or more preferred embodiments of the processes described herein,the polymerization medium includes no more than two phases. That is, thepolymerization medium has a solid phase (e.g., which includes branchedcrystalline polypropylene) and a vapor/liquid phase, which is the phasethat at subcritical conditions would be either a vapor phase or a liquidphase, or both. At supercritical conditions, however, the vapor andliquid phases are indistinguishable. In preferred embodiments, thetemperature is maintained at a level that is sufficiently low so thatthe branched crystalline polypropylene does not melt; thus, at leastsome, or even all, of the products of polymerization are solid.Preferably, the branched crystalline polypropylene produced by thereactions described herein is in particle form, e.g., granules, and thusmay be easily recovered. Preferably, to obtain the solid branchedcrystalline polypropylene, the reaction temperature is maintained belowthe product melting point. For example, the reaction temperature for thesupercritical polymerizations described herein are preferably maintainedat 92° C. or above and 160° C. or below; or more preferably at 95° C. orabove and 155° C. or below.

The terms “two-phase polymerization system” or “two-phase polymerizationmedium” mean a system having two and, preferably, only two phases. Incertain embodiments, the two phases are referenced as a “first phase”and a “second phase.” In certain embodiments, the first phase is orincludes a “monomer phase,” which includes monomers and may also includesolvent and some or all of the product of polymerization, but preferablydoes not include the branched crystalline polypropylene product. Thatis, for example, the monomer phase can be referred to as the “propylenephase.” In certain embodiments, the second phase is or includes a solidphase, which may include products of polymerization, e.g., macromers andcrystalline branched polypropylene, but not monomers, e.g., propylene.As noted above, none of the parts of the catalyst system are consideredto be part of the polymerization medium, although certain parts of thecatalyst system can obviously be solid, e.g., supported catalysts.Furthermore, it is contemplated that parts of the catalyst system may beliquid or vapor or part of the vapor/liquid phase that exists in certainembodiments of the process. Again, however, any part of the catalystsystem is not defined as being part of the polymerization medium.

As used herein, the term “slurry polymerization” means a polymerizationprocess that involves at least two phases, e.g., in which particulate,solid polymer (e.g., granular) is formed in a liquid or vaporpolymerization medium, or in a liquid/vapor polymerization medium.Certain embodiments of the processes described herein are slurrypolymerizations, e.g., processes in which the products of polymerizationare solid. The polymerization products (e.g., polymers) in thoseprocesses preferably have melting points sufficiently high to avoidmelting during polymerization, so that they can in many cases berecovered as granular polymer. A slurry polymerization may includesolvent (i.e., which is also referred to as diluent), or it may be abulk process, discussed below.

As used herein, the term “bulk process” means a polymerization processin which the polymerization medium consists entirely of or consistsessentially of monomers and any products of polymerization that hastaken place, e.g. macromers and polymers, but does not include solvent(i.e., which also means that no diluent is present), or includes minoramounts of solvent, defined as less than 50 volume percent, andpreferably much less.

As used herein, the term “macromer” is defined as a polymeric structurethat contains monomers, e.g., propylene monomer units. A macromer is apolymer with a relatively low molecular weight, in contrast with thefully formed polymer.

The amount of vinyl chain ends is determined by ¹H NMR as set forth inWeng et al., Macromol. Rapid Commun. 2000, 21, 1103-07.

The terms “molecular weight” (M_(n) and M_(w)) and “polydispersity”(Mw/Mn) are intended to broadly encompass molecular weights that areobtained, measured and/or calculated using any published procedure,except to the extent a particular procedure is specified herein.Preferably, the molecular weights are measured in accordance with theprocedure described in the article by T. Sun et al., T. Sun, P. Brant,R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001). For purposes of the claims to this invention, the Mw,Mn, Mz, Mw/Mn are all determined by GPC-DRI as described in T. Sun, P.Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34,Number 19, 6812-6820, (2001).

The “melt flow rate” (MFR) is measured in accordance with ASTM D-1238 at230° C. and 2.16 kg load.

A property that can be used to characterize the branched crystallinepolypropylenes described herein is its heat of fusion (Hf). As usedherein, the heat of fusion is measured using Differential ScanningCalorimetry (DSC), using the ASTM E-794-95 procedure and a DuPontDSC-912. About 10 mg of a sheet of the polymer pressed at approximately230° C. is removed with a punch die and is annealed at room 25° C. for48 hours. At the end of this period, the sample is placed in aDifferential Scanning Calorimeter (Perkin Elmer 7 Series ThermalAnalysis System) and cooled to about −70° C. The sample is heated atabout 10° C./min to attain a final temperature of about 200° C. Thethermal output is recorded as the area under the melting peak of thesample and is reported in Joules per gram as the heat of fusion. Meltingtemperature, 2nd melt, and crystallization temperature are also obtainedusing this DSC procedure.

The term “isotactic” as used herein is defined as referring to a polymersequence in which more than 50% of adjacent monomers having groups ofatoms that are not part of the backbone structure are located either allabove or all below the atoms in the backbone chain, when the latter areall in one plane.

The term “syndiotactic” as used herein is defined as referring to apolymer sequence in which more than 50% of adjacent monomers which havegroups of atoms that are not part of the backbone structure are locatedin some symmetrical fashion above and below the atoms in the backbonechain, when the latter are all in one plane.

The branched polypropylene polymers described herein are characterizedas being “crystalline.” The percent crystallinity (% X) of a propylenepolymer is defined to be: % X=(190 J/g−Hf)/(190 J/g). For purposes ofthis invention the crystallinity of isotactic polypropylene homopolymeris defined herein to be 190 J/g. In preferred embodiments, propylenepolymers produced herein have a percent crystallinity of 30% or more,preferably from 40% to 50%.

As used herein, the term “productivity” is defined as the weight ofpolymer produced per weight of the catalyst used in the polymerizationprocess per 1 hour of polymerization time (e.g., grams polymer/gramcatalyst/hr).

Specific Embodiments of Processes

Certain specific embodiments of the invention will now be discussed. Asdescribed in greater detail below, at least certain embodiments of theprocess result in crystalline branched polypropylene, and yet avoid thenecessity for using diene comonomers, particularly those dienecomonomers that result in gel formation, or for using hydrogen duringpolymerization, and yet provide a branched polypropylene that iscrystalline and has high melt strength and other desirable properties.Furthermore, a branched polypropylene having desired properties ispreferably formed during polymerization, e.g., in the reactor system.Thus, no post-polymerization treatment is required (e.g. no crosslinkingis required to form branching). Also, no substantial amounts of hydrogenneed be added.

In one or more specific embodiments, a process of preparing a polymercomposition that includes branched crystalline polypropylene isdescribed, which includes: contacting a supported metallocene catalystcompound with a polymerization medium that includes propylene monomers;and conducting polymerization of the propylene monomers undersupercritical conditions for a time sufficient to provide branchedcrystalline polypropylene that has from 0.0 wt % to 2.0 wt % ethyleneand a heat of fusion of 70 J/g or more.

Also described is a process of preparing a polymer composition thatincludes branched crystalline polypropylene, which includes: combining ametallocene catalyst compound with propylene monomers in apolymerization medium having less than 30 volume percent diluent;conducting polymerization of the propylene monomers in thepolymerization medium at a reaction temperature that is above thecritical temperature for propylene (91.4° C.), e.g., over 92° C., toform branched crystalline polypropylene; and recovering a branchedcrystalline polypropylene that has from 0.0 wt % to 2.0 wt % ethyleneand a heat of fusion of 70 J/g or more.

Also described is a process of preparing a branched crystallinepolypropylene composition, which includes: contacting a polymerizationmixture that includes propylene monomers and less than 30 volume percentdiluent with a bridged metallocene compound that has at least twoindenyl rings or derivatives of indenyl rings, each ring beingsubstituted at the 2 and 4 positions; and conducting polymerization ofthe propylene monomers under supercritical conditions for a timesufficient to form a branched crystalline polypropylene compositionhaving a heat of fusion of 70 J/g or more.

Also described herein is a process of preparing a branched crystallinepolypropylene composition, which includes: combining a catalyst systemthat includes at least a metallocene compound with a polymerizationmixture that includes propylene monomers and less than 30 volume percentdiluent in a reactor system, and carrying out polymerization of thepropylene monomers in the reactor system under supercritical conditionsfor a time sufficient to form a branched crystalline polypropylene, inwhich: the metallocene compound is represented by the formula:

wherein:

-   -   M¹ is selected from the group consisting of titanium, zirconium,        hafnium, vanadium, niobium, tantalum, chromium, molybdenum and        tungsten;    -   R¹ and R² are identical or different, and are one of a hydrogen        atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl        group, a C₆-C₁₀ aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀        alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl        group, a C₈-C₄₀ arylalkenyl group, an OH group or a halogen        atom; R¹ and R² may also be joined together to form an        alkanediyl group or a conjugated C₄₋₄₀ diene ligand which is        coordinated to M¹ in a metallocyclopentene fashion; R¹ and R²        may also be identical or different conjugated dienes, optionally        substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl        groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups,        said dienes having up to 30 atoms not counting hydrogen and        forming a π complex with M, examples include        1,4-diphenyl-1,3-butadiene, 1,3-pentadiene,        2-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene,        1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene,        1,4-bis(trimethylsilyl)-1,3-butadiene, and        1,4-dinaphthyl-1,3-butadiene;    -   Each R³ is identical or different from the other R³ and is each        a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group which may        be halogenated, a C₆-C₁₀ aryl group which may be halogenated, a        C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀        alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′,        —OR′, —OSiR′₃ or —PR′₂ radical, wherein R′ is one of a halogen        atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;    -   R⁴ to R⁷ are identical or different and are hydrogen, or are as        defined for R³ or two or more adjacent radicals R⁵ to R⁷        together with the atoms connecting them form one or more rings;    -   R¹³ is

—B(R¹⁴)—, ⁻Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴)—;

-   -   wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a        hydrogen atom, a halogen atom, a C₁-C₂₀ branched or linear alkyl        group, a C₁-C₂₀ fluoroalkyl or silaalkyl group, a C₆-C₃₀ aryl        group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, a        C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀        arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵,        together with the atoms binding them, form a cyclic ring;    -   or, R¹³ is represented by the formula:

-   -   wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more        adjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together        with the atoms connecting them form one or more rings;    -   M² is one or more carbons, silicon, germanium or tin; and    -   R⁸, R⁹, R¹⁰, R¹¹ and R¹² are identical or different and have the        meanings stated for R⁴ to R⁷.

In one or more of the processes described herein, the polymerizationmedium can have a first phase that includes propylene monomers and asecond phase that includes the branched crystalline polypropylene.

In one or more of the processes described herein, the polymerizationmedium can have a first phase that includes propylene monomers and asecond phase that includes the branched crystalline polypropylene,wherein the first phase has less than 30 volume percent diluent.

In one or more of the processes described herein, the polymerizationmedium can have a first phase that includes propylene monomers and asecond phase that includes the branched crystalline polypropylene,wherein the second phase is a solid phase.

In one or more of the processes described herein, the polymerizationmedium can have a first phase that includes propylene monomers andmacromers and a second phase that includes the branched crystallinepolypropylene.

In one or more of the processes described herein, the polymerization ofthe propylene monomers is conducted at a pressure of 600 psi (4.14 mPa)or higher. Alternatively, the polymerization can be conducted at apressure of 700 psi (4.83 mPa) or higher. Alternatively, thepolymerization can be conducted at a pressure of 800 psi (15.52 mPa) orhigher.

In one or more of the processes described herein, the polymerization ofthe propylene monomers can be conducted at a temperature of 95° C. orhigher; or at a temperature of 100° C. or higher; or at a temperatureranging from 95° C. to 130° C.

This invention also relates to a process for preparing a polymercomposition comprising: contacting a metallocene catalyst compound witha polymerization medium that includes propylene monomers; and conductingpolymerization of the propylene monomers in the polymerization medium ata reaction temperature of over 92° C.; and recovering polypropylene thathas from 0.0 wt % to 2.0 wt % ethylene, a heat of fusion of 70 J/g ormore, and has a Branching Index of 0.96 or less.

In another preferred embodiment this invention relates to a process toproduce propylene polymers comprising contacting a metallocene catalystcompound and an activator in a reaction medium comprising propylene,from 0 to 30 volume % of one or more solvents and from 0 to 30 mole % ofone or more comonomers, under temperature and pressure conditions belowthe melting point of the propylene polymer and where:

-   -   a) the temperature is at or above the critical temperature for        the reaction medium, and the pressure is at least 500 kPa above        the critical pressure of the reaction medium; or    -   b) the temperature is 1° C. or more above the critical        temperature for the reaction medium, and the pressure is at or        above the critical pressure of the reaction medium; or    -   c) the temperature is 1° C. or more above the critical        temperature for the reaction medium, and the pressure is at        least 500 kPa above the critical pressure of the reaction        medium, provided that when the metallocene catalyst compound is        1,2-ethylene bis(indenyl)zirconium di chloride supported on        silica or the metallocene catalyst compound is        dimethylsilylbis(indenyl) zirconium dichloride supported on        silica then the activator is not methyl alumoxane. Preferably,        the temperature is 2° C. or more above the critical temperature        for the reaction medium, preferably 3° C. or more preferably,        4° C. or more preferably 5° C. or more, preferably 6° C. or        more, preferably 7° C. or more, preferably 8° C. or more,        preferably 9° C. or more, preferably 10° C. or more. Even more        preferably the temperature is between 92 and 200° C., preferably        94 and 160° C., preferably 95 and 155° C., preferably 98 to 150°        C., preferably 100 to 140° C., preferably 100 to 130° C.        Preferably the pressure is 500 kPa or more above the critical        pressure for the reaction medium, preferably 1000 kPa or more,        preferably 1500 kPa or more, preferably 2000 kPa or more,        preferably 2500 kPa or more, preferably 3000 kPa or more,        preferably 3500 kPa or more, preferably 4000 kPa or more,        preferably 4500 kPa or more, preferably 5000 kPa or more. Even        more preferably the pressure is between 4.6 and 10 MPa,        preferably 5.00 and 9 MPa, preferably 5.30 and 8 MPa, preferably        5.50 and 7 MPa. Preferably solvent is present at 0 to 25 vol %,        preferably 0 to 20, preferably 0 to 15 preferably 0 to 10        preferably 0 to 5, preferably, 0 to 4, preferably 0 to 3,        preferably 0 to 2, preferably 0 to 1 vol %. In particularly        preferred embodiments the temperature is between 94 and 130° C.        and the pressure is between 5.0 and 7 MPa.

In one or more of the processes described herein, the branchedcrystalline polypropylene can have a crystallization temperature (Tc) of100° C. or more. Alternatively, the branched crystalline polypropylenecan have a crystallization temperature (Tc) or 105° C. or more.Alternatively, the branched crystalline polypropylene can have acrystallization temperature (Tc) of 110° C. or more; or the branchedcrystalline polypropylene can have a crystallization temperature (Tc)ranging from 105° C. to 110° C.

In one or more of the processes described herein, the branchedcrystalline polypropylene has a melting point (Tm) of 145° C. or more.Alternatively, the branched crystalline polypropylene has a meltingpoint (Tm) of 150° C. or more; or a melting point (Tm) of 155° C. ormore; or a melting point (Tm) of 160° C. or more; or a melting point(Tm) of from 145° C. to 160° C.

In one or more of the processes described herein, the branchedcrystalline polypropylene can have a Melt Flow Rate of 0.5 or more.Alternatively, the branched crystalline polypropylene can have a MeltFlow Rate of 0.7 or more; or a Melt Flow Rate of 1.0 or more; or a MeltFlow Rate of 1.5 or more.

In one or more of the processes described herein, the supportedmetallocene includesdimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconium dimethyl. In afurther alternative, the supported metallocene may includedimethylsilylbis(2-methyl-4-naphthyl-1-indenyl)zirconium dimethyl, andor dimethylsilylbis(2-methyl-4-naphthyl-1-indenyl)zirconium dichloride.

In one or more of the processes described herein, the supportedmetallocene includes a dimethylanilinium tetrakis (perfluorophyl) boronactivator. Alternatively, the supported metallocene includes amethylaluminoxane (MAO).

In one or more of the processes described herein, the polymerizationmedium has less then 25 volume percent diluent; or less then 20 volumepercent diluent; or less then 10 volume percent diluent.

In one or more of the processes described herein, the branchedcrystalline polypropylene has a propylene content of 97 wt % or more. Incertain embodiments, the branched crystalline polypropylene has from 0.0wt % to 0.01 wt % alpha omega dienes.

Preferably, the branched crystalline polypropylene formed by any of theprocesses described herein is isotactic or syndiotactic.

In one or more of the processes described herein, the metallocenecatalyst compound is combined with propylene in the absence of hydrogenor in the presence of hydrogen in an amount of up to 1.0 mole % hydrogenin the reactor.

In one or more of the processes described herein, the heat of fusion ofthe branched crystalline polypropylene is 80 J/g or more. Alternatively,the heat of fusion of the branched crystalline polypropylene is 90 J/gor more. Alternatively, the heat of fusion of the branched crystallinepolypropylene is 100 J/g or more.

In one or more of the processes described herein, the branchedcrystalline polypropylene has a Branching Index of 0.98 or less.Alternatively, the branched crystalline polypropylene has a BranchingIndex of 0.95 or less. Alternatively, the branched crystallinepolypropylene has a Branching Index of 0.90 or less; or a BranchingIndex of 0.80 or less.

In one or more of the processes described herein, the metallocenecatalyst compound is or includes a substituted or unsubstituted silylbridged bis-indenyl metallocene.

In one or more of the processes described herein, the polymerizationmedium includes more than 70% propylene monomers by volume prior to thebeginning of polymerization. Alternatively, the polymerization mediumconsists essentially of propylene monomers. Alternatively, thepolymerization medium consists essentially of monomers and asubstantially inert solvent or diluent. Preferably, the branchedpolypropylene produced by one or more of the processes described hereinis a homopolymer.

Preferred propylene polymers produced typically comprise 0 to 50 mole %of a comonomer, preferably 1 to 40 mole %, preferably 2 to 30 mole %,preferably 4 to 20 mole %, preferably 5 to 15 mole %, preferably 5 to 10mole %, and have a heat of fusion of 70 J/g or more, preferably 75 ormore, preferably 80 or more, preferably 85 or more, preferably 90 ormore, preferably 95 or more, preferably 100 or more, preferably 105 ormore, and a Branching Index (g′_(avg)) of 0.98 or less, preferably 0.97or less, preferably 0.96 or less, preferably 0.95 or less, preferably0.94 or less, preferably 0.93 or less, more preferably 0.92 or less,more preferably 0.91 or less, more preferably 0.90 or less and one ormore of:

-   1. a weight average molecular weight (as measured by GPC DRI) of    20,000 or more, preferably 50,000 to 2,000,000, preferably 100,000    to 1,000,000, preferably 150,000 to 900,000, preferably 200,000 to    800,000;-   2. a melt flow rate of 0.5 dg/min or more, preferably 0.7 dg/min or    more, preferably 1.0 dg/min or more, preferably between 0.1 and 500    dg/min;-   3. a percent crystallinity (% X) of 30% or more, preferably between    40 and 50%;-   4. a melting temperature of 145° C. or more, preferably 150° C. or    more, preferably 155° C. or more, preferably between 145 and 160°    C.;-   5. a crystallization temperature of 100° C. or more, preferably    105° C. or more, preferably 110° C. or more, preferably from 105 to    110° C.;-   6. an Mw/Mn (as measured by GPC DRI) of about 1 to 20, preferably    about 1.5 to 8, preferably 2 to 4; and-   7. a ratio of extensional viscosity at break to linear viscosity of    2.5 or more, preferably 3.0 or more, more preferably 3.5 or more at    strain rates from 0.1 sec⁻¹ to 1.0 sec⁻¹ (as measured using a    Rheometric Scientific RMS-800 in parallel plate oscillatory shear    mode at 180° C. from 0.1 to 400 rad/seconds).    Other Specific Embodiments

An embodiment of a process covered by one or more of the claims belowincludes bulk polymerization of propylene monomers under supercriticalconditions, e.g., at a temperature of 91.7° C. or higher, e.g., 92° C.or above, but preferably 160° C. or lower, to form branched crystallinepolypropylene in situ, e.g., in the reactor system, preferably withoutany post-polymerization treatment. In any one of the bulk polymerizationembodiments, there is preferably no solvent or diluent. Although in someembodiments, minor amounts of solvent or diluent can be present, thoseamounts should be less then 30 percent by volume of the polymerizationmedium, or less than 25 percent by volume, or less than 20 percent byvolume, or less than 20 percent by volume, or less than 15 percent byvolume, or less than 10 percent by volume or less than 5 percent byvolume. The use of large amounts of solvents or diluents in apolymerization reaction can have various disadvantages, such as theadded complexity of the solvent or diluent as well as the fact that thelesser amounts of monomer mean that a substantial amount of the materialin the reactor system is not reactive at all, e.g., inert solvents ordiluents. This in turn can affect the amount and microstructure ofproduct produced.

Preferably, in one or more of the processes described herein, thematerials participating in the polymerization are in two differentphases, so that a two-phase system is employed. Not only are thesupported catalysts part of a solid phase, but so are the branchedcrystalline polypropylene polymers, which are typically present ingranular or particulate form. In certain embodiments, the polymerizationmedium itself (i.e., excluding the catalyst system) is defined as atwo-phase system, with one of the phases (e.g., the first phase) beingreferred to herein as a “monomer phase” (since that phase includes thepropylene monomers) and another of the phases (e.g., the second phase)being referred to a “solid phase,” which includes the branchedcrystalline polypropylene.

Embodiments of the invention include a process for producing branchedpolypropylene by polymerizing propylene monomers above the criticalpoint, i.e., above the critical temperature, and also above the criticalpressure. For example, the polymerization should be conducted attemperatures greater than about 92° C. and at pressures greater thanabout 660 psi (4.55 MPa) in the presence of a supported metallocenecatalyst, which is preferably a single type of metallocene catalyst ofthe type described herein. Preferably, the polypropylene incorporatesbranching during the polymerization reaction (due to the formation ofmacromers having vinyl terminated ends) and no post-polymerizationtreatment is required, e.g., no crosslinking is required to formbranching.

Embodiments of the invention incorporate in-situ branching attemperatures greater than 92° C., preferably greater than 95° C. toproduce polypropylene that is branched, e.g., exhibiting a BranchingIndex (g′_(avg)) of less than 1.0, preferably less than 0.98, morepreferably less than 0.95, and even more preferably less than 0.90 less;or even less than 0.80. Since many of the processes disclosed herein donot require the addition of diene monomers or the use ofpost-polymerization steps, e.g., crosslinking or radiation treatment, toproduce branched polypropylene, the process is advantageously lesscomplicated than other polymerization processes. Nevertheless, ifdesired, certain embodiments of the process may further include theaddition of diene or the use of post-polymerization steps.

As discussed above, certain processes described herein utilizetemperatures and pressures greater than the critical temperature and thecritical pressure for propylene, which are 91.7° C. and 660 psig (4.550MPa), respectively. The critical temperature and pressure are directlyrelated to the density of the monomer, e.g., the propyleneconcentration. Therefore, the polymerization rate of propylene dependson the propylene density. Below the critical point, propylene generallyexists as pure vapor, pure liquid, or coexists as vapor and liquid. Theliquid density of propylene is generally about 4 to about 5 times higherthan density of the corresponding vapor at polymerization temperaturesbelow the critical point, e.g., at about 70° C. At such temperatures,polymer granules are suspended in liquid propylene, and the vapor phasedoes not participate in the reaction. The effective monomerconcentration remains constant as long as liquid propylene is present.As the polymerization temperature increases, the density of saturatedvapor and liquid approach each other and become identical at thecritical point. Therefore, the phase boundary disappears after thecritical point and only single phase exists. As a result, the monomerconcentration in this region depends on the number of moles of monomerin the vessel and the effective monomer density is the average totaldensity, which may be much lower than liquid propylene density.

Although in other processes, higher temperatures generally result inincreased polymerization rates, they also generally cause a substantialdrop in the molecular weight of the polymer product, which is oftenviewed as a disadvantage or shortcoming. Maintaining high molecularweight is desirable for better performance of polypropylene end-useapplications, so achieving such high molecular weight results in aproduct with good properties.

The branched crystalline polypropylenes of the present invention arepreferably polymerized in the presence of supported metallocenecatalysts. As described in greater detail below, the preferredmetallocene catalysts retain high desired activity levels. In preferredembodiments of the processes, the catalyst activity (e.g., for the“second metallocene” described herein) is from 2000 to 8000 g/g; or morenarrowly can be from 3000 to 5000 g/g; or more narrowly still can rangefrom 3000 to 4000 g/g. In preferred embodiments of the processes, theactivity of the second metallocene is greater than 4000 g/g; or greaterthan 5,000 g/g/; or greater than 6,000 g/g.

In one or more embodiments of the process described herein, theresulting BCPP not only has a desired amount of branching, but alsopreferably has a melt flow rate (MFR) within a particular range. Thatrange may have a lower limit of 0.1 dg/min, 0.5 dg/min, or 1.0 dg/min;and the range may have an upper limit of 500 dg/min, 400 dg/min, 300dg/min, 200 dg/min, 100 dg/min, 50 dg/min, or 35 dg/min, with the meltflow rate ranging from any lower limit to any upper limit, depending onwhich claimed invention is being referenced. Moreover, the BCPPpreferably has a polydispersity within a particular range. That rangemay have a lower limit of 1.5 or 2.0, for example; and the range mayhave an upper limit of 15, 10, 8, 7, or 4 with the polydispersityranging from any lower limit to any upper limit, depending on whichclaimed invention is being referenced.

In a preferred embodiment, polymerization of propylene monomers to formbranched polypropylene occurs in a slurry polymerization process, whichcan also be a bulk process, e.g. no solvent present. The polymerizationmedium may include monomers, preferably only propylene monomers, butoptionally also other monomers. However, diene monomers, such asalpha-omega dienes, are typically not be included. Also, while thepolymerization medium prior to polymerization preferably contains onlypropylene, an inert solvent (including diluents) may optionally bepresent, in addition to various additives not directly involved inpolymerization, such as scavengers. The inert solvent may be ahydrocarbon solvent, such as hexane, propane, isobutene, cycloalkane, oraromatic. The polymerization medium preferably includes 30% or morepropylene monomers by volume, more preferably 70% or more propylenemonomers by volume, and even more preferably 95% or more propylenemonomers by volume. Most preferably, the polymerization medium consistsentirely or at least essentially of propylene monomers. Preferably, thepolymerization medium includes 70% or less inert solvent by volume, morepreferably 30% or less inert solvent by volume, and even more preferably5% or less inert solvent by volume. Most preferably, the polymerizationmedium does not contain a significant amount of inert solvent, or doesnot contain any inert solvent.

In at least one preferred embodiment, the only monomer subjected topolymerization, i.e., being part of the polymerization medium, ispropylene. That is, no comonomer, e.g., diene or ethylene or othercomonomers, are included. Also, in that embodiment, the polymerizationmedium is preferably contacted with a metallocene catalyst system(including activators, scavengers, and other compounds that assist inthe catalysis), but the polymerization medium preferably does notcontact (or include) any inert solvent (including any diluent). Thus,neither the propylene monomers nor the resulting macromers nor the finalBCPP product should be dissolved or suspended in liquid other than themonomers or some product of polymerization. It is contemplated that sucha process is of tremendous usefulness in large scale operations sincefewer potential processing problems are likely to develop, e.g.,problems relating to the addition of other materials that in the pasthave been used to provide crosslinking.

As used herein, the term “consisting essentially of” permits a processor composition in which minor amounts of inert or substantiallynon-reactive materials may be added, e.g., 10% by volume or less, ormore preferably 5% or less or even 2% or less by volume. Thus, with thepreferred process, at the beginning of polymerization, thepolymerization medium should include at least about 80% by volumepropylene, preferably 90% or more or more preferably 95% or morepropylene.

In a preferred embodiment, the branched (BCPP) polypropylene is made ofat least 50% propylene units; or at least 60 propylene units; or atleast 70 propylene units; or at least 80 propylene units; or at least 90propylene units; or at least 95 propylene units. More preferably, theBCPP polypropylene is either a homopolymer, consisting of only propyleneunits, or a polymer consisting essentially of propylene units, i.e., apolypropylene having trace or minor amounts of comonomer, includingalpha-omega dienes and one or more alpha-olefins, such as ethylene orC₄-C₂₀ alpha-olefins, cyclics, or aromatics.

Embodiments of the BCPP polypropylene produced have a Branching Index ofless than 1.0, preferably less than 0.98 or 0.95, more preferably lessthan 0.90, and even more preferably less than 0.80. Since the processdisclosed herein does not require the addition of diene monomers or theuse of post-polymerization steps (e.g., cross-linking agents orradiation treatments) to produce branched polypropylene, the process isadvantageously less complicated than other processes. Nevertheless, theprocess may further include the addition of diene or the use ofpost-polymerization steps if increased, or different, branching isdesired.

Embodiments of the BCPP polypropylene also have improved extensionalviscosity, and improved shear thinning behavior in comparison to linearpolypropylene. The BCPP polypropylene preferably has a ratio ofextensional viscosity at break to linear viscosity of at least 2.5, morepreferably at least 3.0, and most preferably at least 3.5 at strainrates from 0.1 second⁻¹ to 1.0 second⁻¹. Thus, the BCPP polypropylenehas improved processability in comparison to linear polypropylene. Ratioof extensional viscosity at break and linear viscosity are determinedare measured using a Rheometric Scientific RMS-800 in parallel plateoscillatory shear mode at 180° C. from 0.1 to 400 rad/seconds.

Embodiments of the BCPP polypropylene have increased melt strength incomparison to linear polypropylene. Thus, the BCPP polypropylene is wellsuited for thermoforming, foaming, blow molding, and other applicationswhich require a melt strength higher than that of linear polypropylene.However, the BCPP polypropylene can be used in various applications,such as thermoforming, foaming, blow molding, extrusion coating, meltblowing, fiber spinning, viscosity modifiers for lube oils, wax crystalmodifiers for hydrocarbon fuels, plasticizers, functionalization ofpolypropylenes, processing aids, thermoplastic elastomers, impactmodifiers, compatibilizers, surface modifiers, wettable polypropylenes,high density polypropylenes, elastic polypropylenes. The BCPPpolypropylene compositions and their blends with other polymers and/ormaterials may be used in any fabricated article, such as films, fibers,sheets, plaques, hoes, belts, tires, tapes, wovens, and otherdimensional objects. The BCPP polypropylene compositions and theirblends with other polymers and/or materials may also be used inradiation resistance articles, for example medical gowns and othermedical garments and applications.

A preferred metallocene compound that is used in the processes describedherein preferably includes or is a silyl-bridged bis-cyclopentadienylmetallocene, and more preferably a bisindenyl metallocene, e.g., asilyl-bridged bis-indenyl metallocene, which may be substituted. Forexample, a silyl-bridged bis-indenyl metallocene that is substituted atthe 2-position and the 4-position is particularly preferred. Preferably,a silyl-bridged bis-indenyl metallocene that is substituted at the2-position with a methyl group and at the 4-position with a phenyl groupis used in the processes described herein. Preferred metallocenecompounds are described in greater detail below, and when used alonepreferably produce isotactic polypropylene.

However, at least certain embodiments of the process involve using ametallocene compound that, when used alone, i.e., without any othercatalyst compound, is capable of producing syndiotactic, rather thanisotactic polypropylene. Syndiotactic producing metallocenes are verywell known in the art. For example, U.S. Pat. Nos. 6,184,326 and4,892,851 describe such metallocenes in detail, along with methods formaking them, and each such description is fully incorporated herein byreference. Common syndio-specific metallocenes are generally acombination of cyclopentadienyl and fluorenyl ligands, which may besubstituted.

Particularly preferred metallocenes are bis-indenyl metallocenes,particularly those having the following general formula:

wherein: M is a metal of Group 4, 5, or 6 of the Periodic Table,preferably zirconium, hafnium and titanium, most preferably zirconium;

-   -   R¹ and R² are identical or different, preferably identical, and        are one of a hydrogen atom, a C₁-C₁₀ alkyl group, preferably a        C₁-C₃ alkyl group, a C₁-C₁₀ alkoxy group, preferably a C₁-C₃        alkoxy group, a C₆-C₁₀ aryl group, preferably a C₆-C₈ aryl        group, a C₆-C₁₀ aryloxy group, preferably a C₆-C₈ aryloxy group,        a C₂-C₁₀ alkenyl group, preferably a C₂-C₄ alkenyl group, a        C₇-C₄₀ arylalkyl group, preferably a C₇-C₁₀ arylalkyl group, a        C₇-C₄₀ alkylaryl group, preferably a C₇-C₁₂ alkylaryl group, a        C₈-C₄₀ arylalkenyl group, preferably a C₈-C₁₂ arylalkenyl group,        or a halogen atom, preferably chlorine; or a conjugated diene        which is optionally substituted with one or more hydrocarbyl,        tri(hydrocarbyl)silyl groups or hydrocarbyl,        tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to        30 atoms not counting hydrogen;    -   R⁵ and R⁶ are identical or different, preferably identical, are        one of a hydrogen atom, a halogen atom, preferably a fluorine,        chlorine or bromine atom, a C₁-C₁₀ alkyl group, preferably a        C₁-C₄ alkyl group, which may be halogenated, a C₆-C₁₀ aryl        group, which may be halogenated, preferably a C₆-C₈ aryl group,        a C₂-C₁₀ alkenyl group, preferably a C₂-C₄ alkenyl group, a        C₇-C₄₀ arylalkyl group, preferably a C₇-C₁₀ arylalkyl group, a        C₇-C₄₀ alkylaryl group, preferably a C₇-C₁₂ alkylaryl group, a        C₈-C₄₀ arylalkenyl group, preferably a C₈-C₁₂ arylalkenyl group,        a —NR₂ ¹⁵, —SR¹⁵, —OR¹⁵, —OSiR₃ ¹⁵ or —PR₂ ¹⁵ radical, wherein:        R¹⁵ is one of a halogen atom, preferably a chlorine atom, a        C₁-C₁₀ alkyl group, preferably a C₁-C₃ alkyl group, or a C₆-C₁₀        aryl group, preferably a C₆-C₉ aryl group;    -   R⁷ is

—B(R¹⁴)—, ⁻Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴)—;

-   -   wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a        hydrogen atom, a halogen atom, a C₁-C₂₀ branched or linear alkyl        group, a C₁-C₂₀ fluoroalkyl or silaalkyl group, a C₆-C₃₀ aryl        group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, a        C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀        arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵,        together with the atoms binding them, form a cyclic ring;    -   preferably, R¹⁴, R¹⁵ and R¹⁶ are identical and are a hydrogen        atom, a halogen atom, a C₁-C₄ alkyl group, a CF₃ group, a C₆-C₈        aryl group, a C₆-C₁₀ fluoroaryl group, more preferably a        pentafluorophenyl group, a C₁-C₄ alkoxy group, in particular a        methoxy group, a C₂-C₄ alkenyl group, a C₇-C₁₀ arylalkyl group,        a C₈-C₁₂ arylalkenyl group, or a C₇-C₁₄ alkylaryl group;    -   or, R⁷ is represented by the formula:

-   -   wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more        adjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together        with the atoms connecting them form one or more rings;        preferably, R¹⁷ to R²⁴ are hydrogen;    -   M² is carbon, silicon, germanium or tin;    -   the radicals R³, R⁴, and R¹⁰ are identical or different and have        the meanings stated for R⁵ and R⁶, or two adjacent R¹⁰ radicals        are joined together to form a ring, preferably a ring containing        from about 4-6 carbon atoms.

Particularly preferred metallocenes are those of the formula:

-   -   wherein: M¹ is selected from the group consisting of titanium,        zirconium, hafnium, vanadium, niobium, tantalum, chromium,        molybdenum and tungsten, preferably zirconium, hafnium or        titanium, most preferably zirconium;    -   R¹ and R² are identical or different, and are one of a hydrogen        atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl        group, a C₆-C₁₀ aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀        alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl        group, a C₈-C₄₀ arylalkenyl group, an OH group or a halogen        atom; R¹ and R² may also be joined together to form an        alkanediyl group or a conjugated C₄₋₄₀ diene ligand which is        coordinated to M¹ in a metallocyclopentene fashion; R¹ and R²        may also be identical or different conjugated dienes, optionally        substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl        groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups,        said dienes having up to 30 atoms not counting hydrogen and        forming a π complex with M, examples include        1,4-diphenyl-1,3-butadiene, 1,3-pentadiene,        2-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene,        1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene,        1,4-bis(trimethylsilyl)-1,3-butadiene, and        1,4-dinaphthyl-1,3-butadiene;    -   preferably R¹ and R² are identical and are a C₁-C₃ alkyl or        alkoxy group, a C₆-C₈ aryl or aryloxy group, a C₂-C₄ alkenyl        group, a C₇-C₁₀ arylalkyl group, a C₇-C₁₂ alkylaryl group, or a        halogen atom, preferably chlorine;    -   R³ are identical or different and are each a hydrogen atom, a        halogen atom, a C₁-C₁₀ alkyl group which may be halogenated, a        C₆-C₁₀ aryl group which may be halogenated, a C₂-C₁₀ alkenyl        group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀ alkylaryl group, a        C₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′, —OR′, —OSiR′₃ or —PR′₂        radical, wherein R′ is one of a halogen atom, a C₁-C₁₀ alkyl        group, or a C₆-C₁₀ aryl group; preferably R³ is not a hydrogen        atom;    -   preferably each R³ is identical and is a fluorine, chlorine or        bromine, atom, a C₁-C₄ alkyl group which may be halogenated, a        C₆-C₈ aryl group which may be halogenated, a —NR′₂, —SR′, —OR′,        —OSiR′₃ or —PR′₂ radical, wherein R′ is one of a chlorine atom,        a C₁-C₄ alkyl group, or a C₆-C₈ aryl group;    -   R⁴ to R⁷ are identical or different and are hydrogen, or are as        defined for R³ or two or more adjacent radicals R⁵ to R⁷        together with the atoms connecting them form one or more rings,        preferably a 6-membered ring, preferably 4-8 membered ring;

—B(R¹⁴)—, ⁻Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴)—;

-   -   wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a        hydrogen atom, a halogen atom, a C₁-C₂₀ branched or linear alkyl        group, a C₁-C₂₀ fluoroalkyl or silaalkyl group, a C₆-C₃₀ aryl        group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, a        C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀        arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵,        together with the atoms binding them, form a cyclic ring;    -   preferably, R¹⁴, R¹⁵ and R¹⁶ are identical and are a hydrogen        atom, a halogen atom, a C₁-C₄ alkyl group, a CF₃ group, a C₆-C₈        aryl group, a C₆-C₁₀ fluoroaryl group, more preferably a        pentafluorophenyl group, a C₁-C₄ alkoxy group, in particular a        methoxy group, a C₂-C₄ alkenyl group, a C₇-C₁₀ arylalkyl group,        a C₈-C₁₂ arylalkenyl group, or a C₇-C₁₄ alkylaryl group;

-   -   or, R¹³ is represented by the formula:    -   wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more        adjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together        with the atoms connecting them form one or more rings;        preferably, R¹⁷ to R²⁴ are hydrogen;    -   M² is one or more carbons, silicon, germanium or tin, preferably        silicon;    -   R¹³ may also be an amidoborane-type radical such as is described        in WO00/20426 (herein fully incorporated by reference); and    -   R⁸, R⁹, R¹⁰, R¹¹ and R¹² are identical or different and have the        meanings stated for R⁴ to R⁷.

In at least one embodiment, the transition metal of the metallocenecompound is preferably zirconium. It is believed that polypropyleneformed using zirconium metallocenes (zirconocenes) have increasedcatalyst activity in comparison to hafnocenes.

Preferred silyl-bridged bis-indenyl metallocenes include silyl-bridgedbis-indenyl zirconocenes, such as the silyl-bridged bis-indenylzirconocenes described above. An example of a preferred silyl-bridgedbis-indenyl zirconocene is dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride. Another example isdimethylsilylbis(2-methyl-4-phenyl indenyl)zirconium dimethyl.

Preferred compounds for use in this invention include metallocenecatalyst compounds represented by the formula: L_(z)(Cp)(Q)M^(m)X_(n)where:

-   Cp is a substituted or unsubstituted cyclopentadienyl ring, a    substituted or unsubstituted indenyl ring or a substituted or    unsubstituted fluoreneyl ring;-   Q is a heteroatom containing group;-   z is 0 or 1;-   L is a bridging group connecting Cp to Q,-   M is a Group 4, 5, or 6 transition metal;-   m is 3, 4, 5 or 6;-   X is a halogen or a substituted or unsubstituted hydrocarbyl group,    a substituted or unsubstituted hydrocarboxy group, or a substituted    or unsubstituted heteroatom containing group; and-   n is m minus 2.

In a preferred embodiment, z is 1, L is represented by the formula:RqSi— where each R is, independently, a substituted or unsubstituted C₁to C₂₀ hydrocarbyl group and q is 1, 2, 3 or 4; and Q is a nitrogencontaining group.

In a preferred embodiment, the metallocene catalyst compound isrepresented by the formula: L_(z)(Cp)₂M^(m)X_(n) where:

-   each Cp is independently a substituted or unsubstituted    cyclopentadienyl ring, a substituted or unsubstituted indenyl ring    or a substituted or unsubstituted fluoreneyl ring;-   z is 0 or 1;-   L is a bridging group connecting Cp to Q,-   M is a Group 4, 5, or 6 transition metal;-   m is 3, 4, 5 or 6;-   X is a halogen or a substituted or unsubstituted hydrocarbyl group,    a substituted or unsubstituted hydrocarboxy group, or a substituted    or unsubstituted heteroatom containing group; and-   n is m minus 2.

In a preferred embodiment, z is 1, L is represented by the formula:

-   RqSi— where each R is, independently, a substituted or unsubstituted    C₁ to C₂₀ hydrocarbyl group and q is 1, 2, 3 or 4; and both Cp    groups are indenyl rings substituted at the 2 and 4 positions.

In a preferred embodiment the metallocene catalyst compound comprisesone or more of:

-   dimethylsiladiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium    dichloride;-   dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium    dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium    dichloride;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium    dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium    dimethyl;-   dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium    dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)    2hafnium dimethyl;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium    dimethyl;-   9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)    2hafnium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-isobutyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)    2hafnium dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium    dichloride;-   dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium    dichloride;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium    dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium    dimethyl;-   dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium    dimethyl;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium    dichloride;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylsiladiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   9-silafluorendiyl(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   dimethylamidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   dimethylamidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-butyl,    4-[3,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   dimethylamidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   diisopropylamidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-propyl,    4-[3,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-ethyl-4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   diisopropylamidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   diisopropylamidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;-   bis(trimethylsilyl)amidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl) η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;-   bis(trimethylsilyl)amidoborane(2-methyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-methyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-ethyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-iso-propyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-n-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-iso-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;-   bis(trimethylsilyl)amidoborane(2-sec-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl; and-   bis(trimethylsilyl)amidoborane(2-tert-butyl,    4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl.    Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound or component which can activate abulky ligand transition metal compound, e.g., any of the metallocenesdefined above. Alumoxane may be used as an activator. A variety ofmethods can be used for preparing alumoxane, non-limiting examples ofwhich are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352,5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827,5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 andEP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and WO 94/10180, each ofwhich is fully incorporated herein by reference. It may be preferable touse a visually clear methylalumoxane. A cloudy or gelled alumoxane canbe filtered to produce a clear solution or clear alumoxane can bedecanted from the cloudy solution.

Also useful in the described processes are ionizing activators, neutralor ionic, or compounds such as dimethylaniliniumtetrakis(perfluorophenyl) boron and tri(n-butyl)ammoniumtetrakis(pentaflurophenyl)boron, which ionize the neutral metallocenecompound. Such ionizing compounds may contain an active proton, or someother cation associated with but not coordinated or only looselycoordinated to the remaining ion of the ionizing compound. Combinationsof activators are also contemplated for use in the process, for example,alumoxane and ionizing activators in combinations, see for example, WO94/07928. In preferred embodiments of the process, dimethylaniliniumtetrakis(perfluorophenyl) boron is used to activate the metallocenecompound, e.g., by affixing the dimethylaniliniumtetrakis(perfluorophenyl) boron to the support, together with themetallocene compound. In preferred embodiments, the support is a silicacompound.

Descriptions of ionic catalysts for coordination polymerizationcomprised of metallocene cations activated by non-coordinating anionsappear in EP-A-0 277 003, EP-A-0 277 004 and U.S. Pat. No. 5,198,401 andWO-A-30 92/00333 (incorporated herein by reference). These teach apreferred method of preparation wherein metallocenes are protonated byan anion precursor such that an alkyl/hydride group is abstracted from atransition metal to make it both cationic and charge-balanced by thenon-coordinating anion.

The term “noncoordinating anion” means an anion which either does notcoordinate to a cation or which is only weakly coordinated to a cationthereby remaining sufficiently labile to be displaced by a neutral Lewisbase. “Compatible” noncoordinating anions are those which are notdegraded to neutrality when the initially formed complex decomposes.Further, the anion will not transfer an anionic substituent or fragmentto the cation so as to cause it to form a neutral four coordinatemetallocene compound and a neutral by-product from the anion.Noncoordinating anions useful in accordance with this disclosure arethose which are compatible, stabilize the metallocene cation in thesense of balancing its ionic charge in a +1 state, yet retain sufficientliability to permit displacement by an ethylenically or acetylenicallyunsaturated monomer during polymerization.

The use of ionizing ionic compounds not containing an active proton butcapable of producing both the active metallocene cation and annoncoordinating anion is also known, see, EP-A-0 426 637 and EP-A-0 573403 (incorporated herein by reference). An additional method of makingthe ionic catalysts uses ionizing anion precursors which are initiallyneutral Lewis acids but form the cation and anion upon ionizing reactionwith the metallocene compounds, for example the use oftris(pentafluorophenyl) boron, see, EP-A-0 520 732 (incorporated hereinby reference). Ionic catalysts for addition polymerization can also beprepared by oxidation of the metal centers of transition metal compoundsby anion precursors containing metallic oxidizing groups along with theanion groups. See, EP-A-0 495 375 (incorporated herein by reference).

Where the metal ligands include halogen moieties (for example,bis-cyclopentadienyl zirconium dichloride) which are not capable ofionizing abstraction under standard conditions, they can be convertedvia known alkylation reactions with organometallic compounds such aslithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignardreagents, etc. See, EP-A-0 500 944 and EP-A1-0 570 982 (incorporatedherein by reference) for in situ processes describing the reaction ofalkyl aluminum compounds with dihalo-substituted metallocene compoundsprior to or with the addition of activating anionic compounds.

Preferred activators for use in this invention include:trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(tert-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tropillium tetraphenylborate,triphenylcarbenium tetraphenylborate, triphenylphosphoniumtetraphenylborate, triethylsilylium tetraphenylborate,benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, andbenzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Mostpreferably, the activator is N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and/ortriphenylcarbenium tetra(perfluorophenyl)borate.

Catalyst Supports.

The metallocenes referenced herein may be supported using a porousparticulate material, such as for example, talc, inorganic oxides,inorganic chlorides and resinous materials such as polyolefin orpolymeric compounds.

Preferred support materials are porous inorganic oxide materials, whichinclude those from the Periodic Table of Elements of Groups 2, 3, 4, 5,13 or 14 metal oxides. Silica, alumina, silica-alumina, and mixturesthereof are particularly preferred. Other inorganic oxides that may beemployed either alone or in combination with the silica, alumina orsilica-alumina are magnesia, titania, zirconia, and the like.

Preferably the support material is porous silica which has a surfacearea in the range of from about 10 to about 700 m²/g, a total porevolume in the range of from about 0.1 to about 4.0 cc/g and an averageparticle size in the range of from about 10 to about 500 μm. Morepreferably, the surface area is in the range of from about 50 to about500 m²/g, the pore volume is in the range of from about 0.5 to about 3.5cc/g and the average particle size is in the range of from about 20 toabout 200 μm. Most preferably the surface area is in the range of fromabout 100 to about 400 m²/g, the pore volume is in the range of fromabout 0.8 to about 3.0 cc/g and the average particle size is in therange of from about 30 to about 100 μm. The average pore size of typicalporous support materials is ≧10 Å. Preferably, a support material isused that has an average pore diameter of ≧50 Å and most preferably itis in the range of from about 75 to about 350 Å. It may be particularlydesirable to dehydrate the silica at a temperature of from about 100° C.to about 800° C. anywhere from about 3 to about 24 hours.

The metallocenes, activator and support material may be combined in anynumber of ways. Suitable support techniques are described in U.S. Pat.Nos. 4,808,561 and 4,701,432 (each fully incorporated herein byreference.). Preferably the metallocenes and activator are combined andtheir reaction product supported on the porous support material asdescribed in U.S. Pat. No. 5,240,894 and WO 94/28034, WO 96/00243, andWO 96/00245 (each fully incorporated herein by reference.)Alternatively, the metallocenes may be preactivated separately and thencombined with the support material either separately or together. If themetallocenes and activator are separately supported, then preferably,they are dried then combined as a powder before use in polymerization.Regardless of whether the metallocene and activator are separatelyprecontacted or whether the metallocene and activator are combined atonce, two or more metallocene compounds may be supported together(co-deposit) or separately (physical blend).

The total volume of reaction solution applied to porous support ispreferably less than about 4 times the total pore volume of the poroussupport, more preferably less than about 3 times the total pore volumeof the porous support and even more preferably in the range of from morethan about 1 to less than about 2.5 times the total pore volume of theporous support. Procedures for measuring the total pore volume of poroussupport are well known in the art. The preferred method is described inVolume 1, Experimental Methods in Catalyst Research, Academic Press,1968, pages 67-96.

Methods of supporting ionic catalysts including metallocene cations andnoncoordinating anions are described in WO 91/09882, WO 94/03506, WO96/04319 and U.S. Pat. No. 5,643,847 (incorporated herein by reference).The methods generally include either physical adsorption on traditionalpolymeric or inorganic supports that have been largely dehydrated anddehydroxylated, or using neutral anion precursors that are sufficientlystrong Lewis acids to activate retained hydroxy groups in silicacontaining inorganic oxide supports such that the Lewis acid becomescovalently bound and the hydrogen of the hydroxy group is available toprotonate the metallocene compounds.

The supported catalyst system may be used directly in polymerization orthe catalyst system may be prepolymerized using methods well known inthe art. The supported catalyst is typically added to the polymerizationmedium as a suspension in mineral oil. For details regardingprepolymerization, see U.S. Pat. Nos. 4,923,833 and 4,921,825, EP 0 279863 and EP 0 354 893 each of which is fully incorporated herein byreference.

For preparation of the branched polypropylene, preactivation of themetallocene may be advantageous. For example, it is widely known in theart that preactivation of the metallocene before addition to acontinuous reactor yields higher activities than continuous addition ofmetallocene and activator in two separate streams. Furthermore, it maybe advantageous to control precontacting time to maximize catalysteffectiveness, e.g., avoiding excessive aging of the activated catalystcomposition.

Monomers

The process described herein may be used for the polymerization ofpropylene and one or more comonomers. Typical comonomers monomersinclude olefins having from 4 to 30 carbon atoms, preferably 4-12 carbonatoms, and more preferably 4 to 8 carbon atoms. Useful monomers includelinear, branched or cyclic olefins; linear, branched or cyclic alphaolefins; linear, branched or cyclic diolefins; linear, branched orcyclic alpha-omega olefins; linear, branched or cyclic polyenes; andlinear, branched or cyclic alpha olefins.

In a preferred embodiment the polymer produced herein is a propylenehomopolymer or copolymer. The comonomer is preferably a C4 to C20linear, branched or cyclic monomer, and in one embodiment is a C4 to C12linear or branched alpha-olefin, preferably butene, pentene, hexene,heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,5-ethyl-1-nonene, 3,5,5-trimethyl-hexene-1, norbornene,norbornadiene, vinyl norbornene, ethylidene norbornene, and the like.Ethylene may be present at 5 mol % or less.

In another embodiment the polymer produced herein is a copolymer of oneor more linear or branched C3 to C30 prochiral alpha-olefins or C5 toC30 ring containing olefins or combinations thereof capable of beingpolymerized by either stereospecific and non-stereospecific catalysts.Prochiral, as used herein, refers to monomers that favor the formationof isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

Useful comonomers also include aromatic-group-containing monomerscontain up to 30 carbon atoms. Suitable aromatic-group-containingmonomers comprise at least one aromatic structure, preferably from oneto three, more preferably a phenyl, indenyl, fluorenyl, or naphthylmoiety. The aromatic-group-containing monomer further comprises at leastone polymerizable double bond such that after polymerization, thearomatic structure will be pendant from the polymer backbone. Thearomatic-group containing monomer may further be substituted with one ormore hydrocarbyl groups including but not limited to C1 to C10 alkylgroups. Additionally two adjacent substitutions may be joined to form aring structure. Preferred aromatic-group-containing monomers contain atleast one aromatic structure appended to a polymerizable olefinicmoiety. Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also useful ascomonomers. These monomers can contain up to 30 carbon atoms. Suitablenon-aromatic cyclic group containing monomers preferably have at leastone polymerizable olefinic group that is either pendant on the cyclicstructure or is part of the cyclic structure. The cyclic structure mayalso be further substituted by one or more hydrocarbyl groups such as,but not limited to, C1 to C10 alkyl groups. Preferred non-aromaticcyclic group containing monomers include vinylcyclohexane,vinylcyclohexene, vinylnorbornene, ethylidene norbornene,cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantaneand the like.

Preferred diolefin comonomers useful in this invention include anyhydrocarbon structure, preferably C4 to C30, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin comonomers be selected from alpha, omega-diene comonomers (i.e.di-vinyl monomers). More preferably, the diolefin comonomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In a preferred embodiment one or more dienes are present in the polymerproduced herein at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

In a preferred embodiment the polymer comprises less than 3 weight %ethylene, preferably less than 2.5 weight %, preferably less than 2weight %, preferably less than 1.5 weight %, preferably less than 1weight %, preferably less than 0.75 weight %, preferably 0.5 weight %,preferably less than 0.25 weight %, preferably less than 0.15 weight %,preferably less than 0.1 weight %.

Reactors

The processes described herein may be used for the polymerization ofpropylene in high-pressure reactors. The most general requirement for asuitable reactor is that the reactor must be substantially unreactivewith the polymerization reaction components. Likewise, the reactor mustbe able to withstand the high pressures and temperatures that occurduring the polymerization reaction. Such reactors are known ashigh-pressure reactors for purposes of this disclosure. Withstandingthese high pressures and temperatures will allow the reactor to maintainthe propylene under supercritical conditions. Suitable reaction vesselsinclude those known in the art to maintain supercritical or otherhigh-pressure ethylene polymerization reactions. Suitable reactors areselected from autoclave, tubular, and autoclave/tubular reactors. Forpurposes of this disclosure, high temperature and pressure are definedas temperatures and pressures greater than the reaction medium'scritical point. Invention processes typically use bulk propylene as thereaction medium. Typically, invention polymerization processes areoperated such that the reaction medium is at high enough temperaturesand pressures so that the medium is in a supercritical state.

In a preferred embodiment the process described herein may be used inautoclave and or tubular reactors. Typically, autoclave reactors havelength-to-diameter ratios of 1:1 to 20:1 and are fitted with ahigh-speed (up to 1500 RPM) multiblade stirrer.

Autoclave pressures are typically greater than 6 MPa. Coupled withthese, maximum autoclave pressures are typically less than 260 MPa. Whenthe autoclave has a low length-to-diameter ratio (such as less than 4)propylene and other monomers are typically injected at only oneposition. But injection at two or more positions in the autoclave isalso possible. For instance, in reactors where the length-to-diameterratio is around 4-20, the reactor can contain up to six differentinjection positions.

Additionally, in the larger (longer) autoclaves, one or more lateralfixing devices support the high-speed stirrer. These fixing devices canalso divide the autoclave into two or more zones. Mixing blades on thestirrer can differ from zone to zone to allow for plug flow or backmixing, largely independently, in the separate zones. Two or moreautoclaves with one or more zones can connect in series to tailorpolymer structure.

A tubular reactor is another reactor type capable of operating up toabout 350 MPa. It is fitted with external cooling and one or moreinjection points along the (tubular) reaction zone. As in autoclaves,these injection points serve as entry points for propylene, one or morecomonomer, catalyst, or mixtures of these. In tubular reactors, externalcooling allows for increased monomer conversion relative to anautoclave, where the low surface-to-volume ratio hinders any significantheat removal. Tubular reactors have a special outlet valve that car,send a pressure shockwave backward along the tube. The shockwave helpsdislodge any polymer residue that has formed on reactor walls duringoperation. Another way of dealing with wall deposits is to fabricate thetube with smooth, polished internal surfaces

Tubular reactors can operate at pressures up to 360 MPa. They havelengths of 100-2000 meters and internal diameters usually less than 10cm.

Reactors that pair autoclaves with tubular reactors can also serve ininvention processes. In such instances, the autoclave typically precedesthe tubular reactor. Such systems may have injection of additionalcatalyst and/or feed components at several points in the autoclave andmore particularly along the tube length.

In both autoclaves and tubular reactors, feeds are injected at or belowroom temperature to provide maximum polymer production within the limitsof maximum operating temperature or within product specifications. Inautoclave operation, a preheater operates at startup, but not after thereaction reaches steady state if the first mixing zone has someback-mixing characteristics. In tubular reactors, the feed is firstheated in a preheater or prewarmer before passing into the cooledsection where reaction takes place.

In both multizone autoclaves and tubular reactors, catalyst can not onlybe injected at the inlet, but also optionally at one or more pointsalong the reactor. The catalyst feeds injected at the inlet and otherinjection points can be the same or different in terms of content,density, concentration, etc. Choosing different catalyst feeds allowspolymer design tailoring.

The autoclave or tubular reactor effluent is depressurized on enteringthe high pressure separator (HPS).

At the reactor outlet valve the pressure drops to begin the separationof polymer and unreacted monomer, co-monomers, propane, etc. Thetemperature in this vessel is typically maintained above the polymerproduct's crystallization point but the pressure may be below thecritical point. The pressure need only be high enough that the propylenecan be condensed against standard cooling water. The liquid recyclestream can then be recycled to the reactor with a liquid pumping systeminstead of the hyper-compressors required for Polyethylene units. Therelatively low pressure in this separator will reduce the monomerconcentration in the liquid polymer phase which will result in a muchlower polymerization rate. This polymerization rate may be low enough tooperate this system without adding a catalyst poison or “killer”. If nopoison is added to the system then the recycle stream will not requiretreating before it can be fed back to the reactors If however a catalystkiller is required (e.g., to prevent reactions in the high pressurerecycle) then provision is preferably made to remove any potentialcatalyst poisons from the recycled propylene rich monomer stream e.g. bythe use of fixed bed adsorbents or by scavenging with an aluminum alkyl.

Alternatively, the HPS may be operated over propylene's criticalpressure but within the propylene/polypropylene two phase region. Thisis an economically preferred method if polypropylene is to be producedwith a revamped HPPE plant. The recycled HPS overhead is cooled anddewaxed before being returned to the suction of the secondarycompressor, which is typical of HPPE plant operation.

The polymer from this intermediate or high pressure vessel will then gothrough another pressure reduction step to a low pressure separator.

In addition to autoclave reactors, tubular reactors, or reactorscombining these, loop-type reactors may be used with the process of thisinvention as well. In this reactor type, monomer enters and polymerexits continuously at different points along the loop, while an in-linepump continuously circulates the contents (reaction liquid). Thefeed/product takeoff rates control total average residence time. Acooling jacket removes reaction heat from the loop.

Industrially a loop reactor is not operated at the high pressuresencountered in autoclaves and tubes. One version of the PP processoperates in a supercritical region but below the cloud point curve ofthe polymer and at temperatures below the polymer crystallization point.Thus the polymer is present as a slurry with the temperature below themelting point of the polymer to avoid fouling deposition of polymer onthe wall thereby reducing heat exchange.

Commercial low pressure loop reactors typically have diameters of 16 to24 inches and lengths of 100 to 200+meters. Operation in a singlesupercritical polypropylene in propylene solution phase typically usespressures of greater than 25 to 30 MPa. At these pressures smallerdiameter thicker wall loop tubing is generally used resulting inpotential difficulties in pump around efficiency and maximum allowablereactor capacity.

In another embodiment, the processes of this invention may be used inthe reactor systems described in U.S. Pat. No. 6,355,741, whichdiscloses a reactor with at least two loops. Invention processes can beused with these two-loop reactors especially, if at least one of theloops uses invention supercritical conditions.

Reaction Conditions

Preferred residence time in high pressure reactors are generally in therange of 15 munites or less, preferably 10 minutes or less, preferably 5minutes or less, more preferably between 30 seconds and 5 minutes.

Feed inlet temperatures are generally at or below room temperature toprovide cooling to the exothermic reaction in the reactor operatingabove the crystallization temperature of the polymer product.

Propylene and higher olefins are far less susceptible to temperaturerunaway and explosive decomposition than ethylene, so potentially ahigher maximum reactor operating temperature can be tolerated but withinthe limits of catalyst activity, molecular weight and isotactivityrequirements of the products.

Pressure

Two phase operation is preferred for production of polymers containingmore long chain branching since a metallocene catalytic complex may bepreferentially soluble in the polymer rich phase allowing chain endincorporation of the terminally unsaturated polypropylene based chainsin subsequent copolymerizations in a propylene starved medium.

Branching may also be favored by running the reaction to conversionsabove 30%.

Comonomers, Dual Catalysts and Polymer Structure

In reactors with multiple injection points for catalyst and feed thereexists the possibility to tailor the polymer design. Use of more thanone catalyst having different molecular weight and structuralcapabilities allows a wide variety of product compositions (e.g.bimodal, linear mixed with long chain branched).

The various olefins will have differing reactivity ratios for a givencatalyst so a plug flow type operation will allow compositional taperingif, for instance, no feeds are injected down the reactor or compensationof the tapering if the more reactive monomer is injected preferentiallyalong the tube. Operation of two autoclaves in series or parallel canallow the use of tailoring by altering the composition of fresh feed tothe second reactor.

Catalyst Killing

The reactor effluent is depressurized to an intermediate pressuresignificantly below the cloud point pressure but neverthelesssupercritical for that composition. This allows separation of a polymerrich phase for further purification and a propylene rich phase forrecycle compression back to the reactor.

This separation is carried out in a vessel known as a high pressureseparator (HPS). Since this vessel also has a significant residencetime, the catalyst activity is typically killed by addition of a polarspecies such as water, alcohol or sodium/calcium stearate. The choiceand quantity of killing agent will depend on the requirements for cleanup of the recycle propylene and comonomers as well as the productproperties, if the killing agent has low volatility.

Alternatively the intermediate separation can be done at pressures wellbelow the critical point so that the monomer concentration and thereforereactivity in the high pressure separator is relatively low. Therelatively small amount of continued polymerization in this vessel maynot be a problem, so addition of catalyst deactivating compounds may beavoided presuming that no undesired reactions occur in the high orintermediate pressure recycle system. If no killing compounds are addedthen the killer removal step can be eliminated.

Choice of Propylene Feed Purity

Propylene is available commercially at two levels of purity—polymergrade at 99.5% and chemical grade at about 93 to 95%. The choice of feedwill set the level of purge required from the recycle to avoid overdilution of the feed by inert propane. The presence of propane in thereactor and HPS will raise the pressure of the cloud point curve for agiven temperature but will decrease the polymerization efficiency due toa decrease in propylene (and other olefin) concentrations in thereactor. The elevation of cloud point pressure due to propane will widenthe operating window of the HPS. In copolymerizations of propylene withlimited amounts of ethylene, a similar effect in raising the cloud pointpressure will be noted due to the presence of low levels of ethylene inthe HPS.

Low Pressure Separator Operation

The LPS running at just above atmospheric pressure is a sub criticalflash of light components, reactants and oligomers thereof, for thepurpose of producing a low volatile containing polymer melt entering thefinishing extruder or static mixer.

Applications

The polymer compositions of this invention (and blends thereof asdescribed above) may be used in any known thermoplastic or elastomerapplication. Examples include uses in molded parts, films, tapes,sheets, tubing, hose, sheeting, wire and cable coating, adhesives,shoesoles, bumpers, gaskets, bellows, films, fibers, elastic fibers,nonwovens, spunbonds, sealants, surgical gowns and medical devices.

Adhesives

The polymers of this invention or blends thereof can be used asadhesives, either alone or combined with tackifiers. Preferredtackifiers are described above. The tackifier is typically present atabout 1 weight % to about 50 weight %, based upon the weight of theblend, more preferably 10 weight % to 40 weight even more preferably 20weight % to 40 weight %. Other additives, as described above, may beadded also.

The adhesives of this invention can be used in any adhesive application,including but not limited to, disposables, packaging, laminates,pressure sensitive adhesives, tapes labels, wood binding, paper binding,non-wovens, road marking, reflective coatings, and the like. In apreferred embodiment the adhesives of this invention can be used fordisposable diaper and napkin chassis construction, elastic attachment indisposable goods converting, packaging, labeling, bookbinding,woodworking, and other assembly applications. Particularly preferredapplications include: baby diaper leg elastic, diaper frontal tape,diaper standing leg cuff, diaper chassis construction, diaper corestabilization, diaper liquid transfer layer, diaper outer coverlamination, diaper elastic cuff lamination, feminine napkin corestabilization, feminine napkin adhesive strip, industrial filtrationbonding, industrial filter material lamination, filter mask lamination,surgical gown lamination, surgical drape lamination, and perishableproducts packaging.

Films

The compositions described above and the blends thereof may be formedinto monolayer or multilayer films. These films may be formed by any ofthe conventional techniques known in the art including extrusion,co-extrusion, extrusion coating, lamination, blowing and casting. Thefilm may be obtained by the flat film or tubular process which may befollowed by orientation in an uniaxial direction or in two mutuallyperpendicular directions in the plane of the film. One or more of thelayers of the film may be oriented in the transverse and/or longitudinaldirections to the same or different extents. This orientation may occurbefore or after the individual layers are brought together. For examplea polyethylene layer can be extrusion coated or laminated onto anoriented polypropylene layer or the polyethylene and polypropylene canbe coextruded together into a film then oriented. Likewise, orientedpolypropylene could be laminated to oriented polyethylene or orientedpolyethylene could be coated onto polypropylene then optionally thecombination could be oriented even further. Typically the films areoriented in the Machine Direction (MD) at a ratio of up to 15,preferably between 5 and 7, and in the Transverse Direction (TD) at aratio of up to 15 preferably 7 to 9. However in another embodiment thefilm is oriented to the same extent in both the MD and TD directions.

In another embodiment the layer comprising the polyolefin composition ofthis invention (and/or blends thereof) may be combined with one or moreother layers. The other layer(s) may be any layer typically included inmultilayer film structures. For example the other layer or layers maybe:

1. Polyolefins

Preferred polyolefins include homopolymers or copolymers of C2 to C40olefins, preferably C2 to C20 olefins, preferably a copolymer of analpha-olefin and another olefin or alpha-olefin (ethylene is defined tobe an alpha-olefin for purposes of this invention). Preferablyhomopolyethylene, homopolypropylene, propylene copolymerized withethylene and or butene, ethylene copolymerized with one or more ofpropylene, butene or hexene, and optional dienes. Preferred examplesinclude thermoplastic polymers such as ultra low density polyethylene,very low density polyethylene, linear low density polyethylene, lowdensity polyethylene, medium density polyethylene, high densitypolyethylene, polypropylene, isotactic polypropylene, highly isotacticpolypropylene, syndiotactic polypropylene, random copolymer of propyleneand ethylene and/or butene and/or hexene, elastomers such as ethylenepropylene rubber, ethylene propylene diene monomer rubber, neoprene, andblends of thermoplastic polymers and elastomers, such as for example,thermoplastic elastomers and rubber toughened plastics.

2. Polar Polymers

Preferred polar polymers include homopolymers and copolymers of esters,amides, acetates, anhydrides, copolymers of a C2 to C20 olefin, such asethylene and/or propylene and/or butene with one or more polar monomerssuch as acetates, anhydrides, esters, alcohol, and or acrylics.Preferred examples include polyesters, polyamides, ethylene vinylacetate copolymers, and polyvinyl chloride.

3. Cationic Polymers

Preferred cationic polymers include polymers or copolymers of geminallydisubstituted olefins, alpha-heteroatom olefins and/or styrenicmonomers. Preferred geminally disubstituted olefins include isobutylene,isopentene, isoheptene, isohexane, isooctene, isodecene, andisododecene. Preferred alpha-heteroatom olefins include vinyl ether andvinyl carbazole, preferred styrenic monomers include styrene, alkylstyrene, para-alkyl styrene, alpha-methyl styrene, chloro-styrene, andbromo-para-methyl styrene. Preferred examples of cationic polymersinclude butyl rubber, isobutylene copolymerized with para methylstyrene, polystyrene, and poly-alpha-methyl styrene.

4. Miscellaneous

Other preferred layers can be paper, wood, cardboard, metal, metal foils(such as aluminum foil and tin foil), metallized surfaces, glass(including silicon oxide (SiO.x) coatings applied by evaporating siliconoxide onto a film surface), fabric, spunbonded fibers, and non-wovens(particularly polypropylene spun bonded fibers or non-wovens), andsubstrates coated with inks, dyes, pigments, and the like.

The films may vary in thickness depending on the intended application,however films of a thickness from 1 to 250 μm are usually suitable.Films intended for packaging are usually from 10 to 60 micron thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

Additives such as block, antiblock, antioxidants, pigments, fillers,processing aids, UV stabilizers, neutralizers, lubricants, surfactantsand/or nucleating agents may also be present in one or more than onelayer in the films. Preferred additives include silicon dioxide,titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calciumsterate, carbon black, low molecular weight resins and glass beads.

In another embodiment one more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, or microwaveirradiation. In a preferred embodiment one or both of the surface layersis modified by corona treatment.

The films described herein may also comprise from 5 to 60 weight %,based upon the weight of the polymer and the resin, of a hydrocarbonresin. The resin may be combined with the polymer of the seal layer(s)or may be combined with the polymer in the core layer(s). The resinpreferably has a softening point above 100° C., even more preferablyfrom 130 to 180° C. Preferred hydrocarbon resins include those describedabove. The films comprising a hydrocarbon resin may be oriented inuniaxial or biaxial directions to the same or different degrees.

Molded Products

The polyolefin composition described above may also be used to preparethe molded products of this invention in any molding process, includingbut not limited to, injection molding, gas-assisted injection molding,extrusion blow molding, injection blow molding, injection stretch blowmolding, compression molding, rotational molding, foam molding,thermoforming, sheet extrusion, and profile extrusion.

The compositions described herein may be shaped into desirable end usearticles by any suitable means known in the art. Thermoforming, vacuumforming, blow molding, rotational molding, slush molding, transfermolding, wet lay-up or contact molding, cast molding, cold formingmatched-die molding, injection molding, spray techniques, profileco-extrusion, or combinations thereof are typically used methods.

Blow molding is another suitable forming means, which includes injectionblow molding, multi-layer blow molding, extrusion blow molding, andstretch blow molding, and is especially suitable for substantiallyclosed or hollow objects, such as, for example, gas tanks and otherfluid containers. Blow molding is described in more detail in, forexample, Concise Encyclopedia of Polymer Science and Engineering 90-92(Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).

The polymer compositions described above may also be used to preparenonwoven fabrics and fibers in any nonwoven fabric and fiber makingprocess, including but not limited to, melt blowing, spunbonding, filmaperturing, and staple fiber carding. A continuous filament process mayalso be used. Preferably a spunbonding process is used. The spunbondingprocess involves the extrusion of fibers through a spinneret. Thesefibers are then drawn using high velocity air and laid on an endlessbelt. A calender roll is generally then used to heat the web and bondthe fibers to one another although other techniques may be used such assonic bonding and adhesive bonding. The fabric may be prepared withmixed metallocene polypropylene alone, physically blended with othermixed metallocene polypropylene or physically blended with singlemetallocene polypropylene. Likewise the fabrics of this invention may beprepared with mixed metallocene polypropylene physically blended withconventional Ziegler-Natta produced polymer. If blended, the fabric ofthis invention is preferably comprised of at least 50% mixed metallocenepolypropylene. With these nonwoven fabrics, manufacturers can maintainthe desirable properties of fabrics prepared with metallocene producedpolypropylene while increasing fabric strength and potentially increasedline speed compared to fabrics made using conventional polymers.

EXAMPLES Example 1

In the following example, various samples of polypropylene were formedusing two different metallocene catalysts at similar polymerizationconditions. The properties of the samples are reflected in Table 1.

The results in Table 1 demonstrate the dramatically superior resultsthat were obtained using the indenyl metallocene having substitutions atthe 2- and 4-positions, as opposed to using an indenyl metallocene thatwas unsubstituted at the 4-position. Specifically, the activities of thecatalysts used in forming Samples 3 and 4 were almost ten times as highas the activities of the catalysts used in forming Samples 1 and 2.Also, the results show the further improvement in catalyst activity dueto conducting polymerization under supercritical conditions (Sample 4)in comparison with polymerization under subcritical conditions (Sample3). Also noteworthy was the fact that the supercritical conditions didnot cause any significant deterioration of melting point Tm.

Sample 1 was prepared from 1000 ml of propylene and 0.2 g of 20% ofdimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride activated bymethylaluminumoxane activator supported on silica (Catalyst A). Sample 2was prepared from 1000 ml of propylene and 0.2 g of 20% ofdimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride (Catalyst B).Sample 3 was prepared from 1000 ml of propylene and 0.45 g of 20% ofdimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconium dimethyl(Catalyst C). Sample 4 was prepared from 1000 ml of propylene and 0.45 gof 20% or dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconiumdimethyl (Catalyst D).

Each polymerization was conducted separately in a batch reactor with thestirrer set at 800 rpm for 60 min. The propylene was added in twointervals. First, 800 ml of propylene at room temperature was added tothe reactor. The catalyst was then flushed with 200 ml of propylene atroom temperature and introduced to the reactor through a catalyst tube(1 ml of white oil was added to the catalyst tube). Triethyl aluminumscavenger (1 ml, 25 wt % in toluene) was charged to the reactor througha stainless steel tube. Each of the polypropylene samples wascharacterized using H NMR, DSC, and GPC methods. The amount of vinylchain ends is determined by ¹H NMR as set forth in Weng et al.,Macromol. Rapid Commun. 2000, 21, 1103-07.reference on p.14. Themolecular weight data (M_(n), M_(w), M_(z)) and MWD were obtained fromGPC-DRI and GPC-VIS methods. Branching was measured using GPC-MALLS andare reported as “g” at each molecular weight in the GPC trace. Relatingthe measured g to branched structure requires the application ofZimm-Stockmayer theory, which assumes a random distribution of branchsizes for each population of branched structures (singly, doubly, triplybranched, etc.) at each molecular weight as described by B. H. Zimm andW. H. Stockmayer, J. Chem. Phys. 17, 1301 (1949). The glass transitiontemperature (Tg) and melting point data were collected on a DuPont DSC912 instrument with thin molded film samples, scanning at 10° C./min.The melting temperatures reported were obtained from the second melt.The rheology test samples were compression molded at 180-190° C. with0.1-0.2 weight percent BHT/B225 stabilizer added to the powder samples.The complex viscosity measurements were done by subjecting these samplesto a frequency sweep from 0.01 rad/s to 390 rad/s in dynamic oscillatorymode using 10% strain. The extensional viscosity data was collected byusing a Rheometrics Scientific ARES at 190° C. The MFR measurements(ASTM 1238) were made using the MI instrument (BPC L121) at 190° C.under 2.06 kg load.

TABLE 1 Catalyst Tem- Activity g′ - Sam- per- Pressure (g polymer/average ple Catalyst ature (bar/MPa) g cat/hr) T_(m) (° C.) (viscosity)1 A 70 34.2/3.4  135 — — 2 B 93.9  53/5.3 290 145.1 — 3 C 70  35/3.51,933 149.4 1.017 4 D 94.5 53.4/5.3  2,597 148.4 0.970

Example 2

In the following example, various samples of polypropylene were formedusing different polymerization conditions. The properties of the samplesare reflected in Table 2.

Identical samples of polypropylene were prepared from 1000 ml ofpropylene and dimethylsilylbis(2-methyl-4-phenyl-1-indenyl)zirconiumdimethyl in combination with dimethylanilinium tetrakis(perfluorophenyl) boron activator (Catalyst E). High purity liquidpropylene monomer (99.5%) was purchase from Matheson and furtherpurified by passing the propylene monomer through a mole sieve columncommercially available from Matheson, Texas and an oxygen removal columncommercially available from Labclear, California.

Each polymerization was conducted separately in a batch reactor with thestirrer set at 800 rpm for 60 min. The propylene was added in twointervals. First, 800 ml of propylene at room temperature was added tothe reactor. The catalyst (10.04 wt % in white oil prepared usingDavison 952 silica calcined at 600° C.) was then flushed with 200 ml ofpropylene at room temperature and introduced to the reactor through acatalyst tube (1 ml of white oil was added to the catalyst tube).Triethyl aluminum scavenger, (1 ml, 25 wt % in toluene) was charged tothe reactor through a stainless steel tube.

All polymerizations were conducted in a high pressure RC-1 reactioncalorimeter commercially available from Mettler. The reactor wasrecertified to 1176 psi (8.11 MPa) at a maximum operating temperature of175° C. to accommodate the planned experiments. Each of thepolypropylene samples was characterized using H NMR, DSC, Ml, meltrheology, and GPC methods described above.

TABLE 2 Sample 5 6 7 8 9 10 Temperature 75 80 85 90 93 95 (° C.)Pressure (psi) 500 542 597 674 707 725 Vinyl (%) 6 7 11 13 19 15 GPC-DRIM_(w) (k) 822 623 600 520 450 458 M_(n) (k) 361 260 231 202 154 158 PD2.3 2.4 2.6 2.6 3.0 2.9 GPC-VIS M_(w) (k) 802 644 600 520 450 514 M_(n)(k) 248 238 231 202 154 165 PD 3.2 2.7 2.6 2.6 3.0 3.1 Branching 0.9940.971 0.960 0.947 0.933 0.934 Index (g′) DSC (° C.) T_(m) 149 148 150146 150 151 T_(c) 111 106 109 106 109 108 MFR (dg/mir) 0.3 0.3 0.3 0.71.6 1.7

The results demonstrate improved properties of Samples 9 and 10, i.e.,polypropylene prepared under supercritical conditions, over theproperties of Samples 5-8, i.e., polypropylene prepared undersubcritical conditions. All the samples were prepared using identicalcatalyst systems and monomer concentration; the only variables weretemperature and pressure. The branching and melt flow rates weresubstantially higher for Samples 9 and 10 than for Samples 5-8,demonstrating the improved results due to the use of supercriticalconditions.

1. A process of preparing a branched homopropylene compositioncomprising: contacting a polymerization mixture that comprises propylenemonomers with a metallocene catalyst compound having at least twoindenyl rings or derivative of indenyl rings, wherein each ring issubstituted at the 2 and 4 positions, activated with a non-coordinatinganion, under temperature and pressure conditions below the melting pointof the propylene polymer and where: a) the temperature is at or abovethe critical temperature for the reaction medium, and the pressure is atleast 500 kPa above the critical pressure of the reaction medium; or b)the temperature is 1° C. or more above the critical temperature for thereaction medium, and the pressure is at or above the critical pressureof the reaction medium; or c) the temperature is 1° C. or more above thecritical temperature for the reaction medium, and the pressure is atleast 500 kPa above the critical pressure of the reaction medium, andconducting polymerization of the propylene monomers for a timesufficient to form the branched homopropylene composition having a heatof fusion of 70 J/g, a T_(m) of 145° C. or more and a branching index(g′) of 0.97 or less.
 2. The process of claim 1 wherein the temperatureis 2° C. or more above the critical temperature for the reaction medium.3. The process of claim 1 wherein the temperature is between 94 and 160°C.
 4. The process of claim 1 wherein the pressure is 1000 kPa or moreabove the critical pressure for the reaction medium.
 5. The process ofclaim 1 wherein the pressure is between 5.0 and 9 MPa.
 6. The process ofclaim 1 wherein the temperature is between 94 and 130° C. and thepressure is between 5.0 and 7 MPa.
 7. The process of claim 1 whereinsolvent is present at 0 to 15 vol %.
 8. The process of claim 1 where themetallocene catalyst compound is represented by the formula:L_(z)(Cp)₂M^(m)X_(n) where: each Cp is independently a substitutedindenyl ring wherein each ring is substituted at the 2 and 4 positions;z is 0 or 1; L is a bridging group connecting Cp to Cp, M is a Group 4,5, or 6 transition metal; m is 3, 4, 5 or 6; X is a halogen or asubstituted or unsubstituted hydrocarbyl group, a substituted orunsubstituted hydrocarboxy group, or a substituted or unsubstitutedheteroatom containing group; and n is m minus
 2. 9. The process of claim8 wherein z is 1, L is represented by the formula: RqSi-where each R is,independently, a substituted or unsubstituted C₁ to C₂₀ hydrocarbylgroup and q is 1, 2, 3 or 4; and both Cp groups are indenyl ringssubstituted at the 2 and 4 positions.
 10. The process of any of claims 1to 7 wherein the metallocene catalyst compound comprises one or more of:dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-iso-propyl-4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl,4-[3,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-isobutyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;9-silafluorendiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl 9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl; 9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdichloride; dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdichloride; dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumdimethyl; dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl; dimethyldimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumdimethyl; dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyldiisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethylbis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl; andbis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl.
 11. The process ofclaim 1 where the metallocene compound is represented by the formula:

wherein: M¹ is selected from the group consisting of titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten; R¹ and R² are identical or different, and are one of ahydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀aryl group, a C₆-C₁₀ aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, aC₉-C₄₀ arylalkenyl group, an OH group or a halogen atom; R¹ and R² mayalso be joined together to form an alkanediyl group or a conjugatedC₄₋₄₀ diene ligand which is coordinated to M¹ in a metallocyclopentenefashion; R¹ and R² may also be identical or different conjugated dienes,optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl)silyl groups or hydrocarbyl,tri(hydrocarbyl)silylhydrocarbyl groups, said dienes having up to 30atoms not counting hydrogen and forming a .pi. complex with M; each R³is identical or different from the other R³ and is each a halogen atom,a C₁-C₁₀ alkyl group which may be halogenated, a C₆-C₁₀ aryl group whichmay be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkyl group, aC₇-C₄₀ alkylaryl group, a C₉-C₄₀ arylalkenyl group, a —NR′₂, —SR′, —OR′,—OSiR′₃ or —PR′₂ radical, wherein R′ is one of a halogen atom, a C₁-C₁₀alkyl group, or a C₆-C₁₀ aryl group; R⁴ to R¹² are identical ordifferent and are hydrogen, or are as defined for R³ or two or moreadjacent radicals R⁵ to R⁷ together with the atoms connecting them formone or more rings;

—B(R¹⁴)—, ⁻Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴)—; wherein: R¹⁴, R¹⁵ and R¹⁶ are identical ordifferent and are a hydrogen atom, a halogen atom, a C₁-C₂₀ branched orlinear alkyl group, a C₁-C₂₀ fluoroalkyl or silaalkyl group, a C₆-C₃₀aryl group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, a C₂-C₂₀alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀ arylalkenyl group, aC₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵, together with the atoms bindingthem, form a cyclic ring; or, R¹³ is represented by the formula;

wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings; and M² is one or morecarbons, silicon, germanium or tin.
 12. The process of claim 1 where themetallocene catalyst compound having at least two indenyl rings orderivative of indenyl rings, wherein each ring is substituted at the 2and 4 positions and is a substituted or unsubstituted silyl bridgedbis-indenyl metallocene.
 13. The process of claim 1 where themetallocene catalyst compound is combined with propylene in an amount ofup to 1.0 mole % hydrogen in the reactor.
 14. The process of claim 1wherein the activator comprises alumoxane.
 15. The process of claim 1wherein the activator is selected from the group consisting of:trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(tert-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,di-(iso-propyl)ammonium tetrakis(pentafluorophenyl)borate,dicyclohexylammonium tetrakis(pentafluorophenyl)borate;tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, andbenzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. 16.The process of claim 1 wherein the activator comprises one or more of:dimethylanilinium tetrakis(perfluorophenyl)boron, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)boron, N,N-dimethylaniliniumtetra(perfluorophenyl)borate and/or triphenylcarbeniumtetra(perfluorophenyl)borate.
 17. The process of claim 1 where thecatalyst compound, the activator or both are supported.
 18. The processof claim 17 wherein the support comprises silica.
 19. The process ofclaim 1 wherein the process occurs in an autoclave reactor.
 20. Theprocess of claim 1 wherein the process occurs in a tubular reactor. 21.The process of claim 1 wherein the process occurs in a loop reactor. 22.The process of claim 1 wherein the polymerization medium comprises atleast two phases.
 23. The process of claim 1 wherein the catalystactivity is at least 2597 grams of polymer per gram of catalyst perhour.